Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen

ABSTRACT

The present invention provides a polymerization process utilizing a dual metallocene catalyst system for the production of broad or bimodal molecular weight distribution polymers, generally, in the absence of added hydrogen. Polymers produced from the polymerization process are also provided, and these polymers can have a Mn in a range from about 9,000 to about 30,000 g/mol, and a short chain branch content that decreases as molecular weight increases.

BACKGROUND OF THE INVENTION

The present invention relates generally to the field of olefinpolymerization catalysis, metallocene catalyst compositions, methods forthe polymerization and copolymerization of olefins, and polyolefins.More specifically, this invention relates to dual catalyst systems forproducing broad or bimodal molecular weight distribution polyolefins inthe absence of added hydrogen.

Broad or bimodal molecular weight distribution polyolefins(homopolymers, copolymers, terpolymers, and the like) can be producedusing various combinations of catalyst systems and polymerizationprocesses. Such broad or bimodal molecular weight distributionpolyolefins may be produced using a dual metallocene catalyst system,but often requiring the presence of added hydrogen in order to do so.The addition of hydrogen gas to certain polymerization reactor systems,however, may adversely affect reactor operating conditions, as well asthe resulting properties of the polymer produced, for example, polymermolecular weight or melt index.

It would be beneficial to produce broad or bimodal molecular weightdistribution polyolefins using a metallocene-based dual catalyst systemthat does not require the addition of hydrogen to the polymerizationreactor. Accordingly, it is to this end that the present invention isdirected.

SUMMARY OF THE INVENTION

The present invention discloses polymerization processes employing dualcatalyst systems for the production of broad and/or bimodal polymers,generally in the absence of added hydrogen.

In accordance with one aspect of the present invention, a catalystcomposition is provided, and this catalyst composition comprisescatalyst component I, catalyst component II, and an activator. Inanother aspect, an olefin polymerization process is provided and, inthis aspect, the process comprises contacting a catalyst compositionwith an olefin monomer and optionally an olefin comonomer underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises catalyst component I, catalyst componentII, and an activator.

In these catalyst compositions and polymerization processes, catalystcomponent I can comprise:

-   -   a compound having formula (A);    -   a compound having formula (B);    -   a dinuclear compound formed from an alkenyl-substituted compound        having formula (A), formula (B), or a combination thereof; or    -   any combination thereof, wherein:        formula (A) is

wherein:

-   -   M¹ is Zr or Hf;    -   X¹ and X² are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms;    -   E¹ is C or Si;    -   R¹ and R² are independently H, a hydrocarbyl group having up to        18 carbon atoms, or R¹ and R² are connected to form a cyclic or        heterocyclic group having up to 18 carbon atoms; and    -   R³ is H or a hydrocarbyl or hydrocarbylsilyl group having up to        18 carbon atoms; and        formula (B) is

wherein:

-   -   M² is Zr or Hf;    -   X³ is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or        SO₃R, wherein R is an alkyl or aryl group having up to 18 carbon        atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or        a hydrocarbylsilyl group, any of which having up to 18 carbon        atoms;    -   E² is C or Si;    -   R⁴ is H or a hydrocarbyl group having up to 18 carbon atoms; and    -   R⁵ is a hydrocarbyl or hydrocarbylsilyl group having up to 18        carbon atoms.

In these catalyst compositions and polymerization processes, catalystcomponent II can comprise:

-   -   a compound having formula (C);    -   a compound having formula (D);    -   a compound having formula (E);    -   a compound having formula (F);    -   a dinuclear compound formed from an alkenyl-substituted compound        having formula (C), formula (D), formula (E), formula (F), or a        combination thereof; or    -   any combination thereof, wherein:        formula (C) is

wherein:

-   -   M³ is Zr or Hf;    -   X⁴ and X⁵ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms;    -   E³ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >E^(3A)R^(7A)R^(8A),            wherein E^(3A) is C or Si, and R^(7A) and R^(8A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula            —CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B), R^(8B),            R^(7C), and R^(8C) are independently H or a hydrocarbyl            group having up to 10 carbon atoms, or        -   a bridging group having the formula            —SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—, wherein R^(7D), R^(8D),            R^(7E), and R^(8E) are independently H or a hydrocarbyl            group having up to 10 carbon atoms;    -   R⁹ and R¹⁰ are independently H or a hydrocarbyl group having up        to 18 carbon atoms; and    -   Cp¹ is a cyclopentadienyl or indenyl group, any substituent on        Cp¹ is H or a hydrocarbyl or hydrocarbylsilyl group having up to        18 carbon atoms;        formula (D) is

wherein:

-   -   M⁴ is Zr or Hf;    -   X⁶ and X⁷ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms;    -   E⁴ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >R^(4A)R^(12A)R^(13A),            wherein E^(4A) is C or Si, and R^(12A) and R^(13A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula            —CR^(12B)R^(13B)—CR^(12C)R^(13C)—, wherein R^(12B), R^(13B),            R^(12C), and R^(13C) are independently H or a hydrocarbyl            group having up to 10 carbon atoms, or        -   a bridging group having the formula            —SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, wherein R^(12D),            R^(13D), R^(12E), and R^(13E) are independently H or a            hydrocarbyl group having up to 10 carbon atoms; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are independently H or a hydrocarbyl        group having up to 18 carbon atoms;        formula (E) is

wherein:

-   -   M⁵ is Zr or Hf;    -   X⁸ and X⁹ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms; and    -   E⁵ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >E^(5A)R^(20A)R^(21A),            wherein E^(5A) is C or Si, and R^(20A) and R^(21A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula —(CH₂)_(n)—, wherein n            is an integer from 2 to 6, inclusive, or        -   a bridging group having the formula            —SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—, wherein R^(20B),            R^(21B), R^(20C), and R^(21C) are independently H or a            hydrocarbyl group having up to 10 carbon atoms; and            formula (F) is

wherein:

-   -   M⁶ is Zr or Hf;    -   X¹⁰ and X¹¹ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms; and    -   Cp² and Cp³ are independently a cyclopentadienyl, indenyl or        fluorenyl group, any substituent on Cp² and Cp³ is independently        H or a hydrocarbyl group having up to 18 carbon atoms.

Polymers produced from the polymerization of olefins using thesecatalyst systems, resulting in homopolymers, copolymers, and the like,can be used to produce various articles of manufacture. In some aspectsof this invention, an ethylene polymer produced herein can becharacterized as having the following polymer properties: a broad and/ora bimodal molecular weight distribution (MWD); and/or a Mn in a rangefrom about 9,000 to about 30,000 g/mol; and/or a ratio of Mw/Mn fromabout 4 to about 20; and/or a short chain branch content that decreasesas molecular weight increases.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates the definitions of D90 and D10 on a molecular weightdistribution curve.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 1-4.

FIG. 3 presents a plot of the molecular weight distributions of thepolymers of Examples 5-6.

FIG. 4 presents a plot of the molecular weight distributions of thepolymers of Examples 7-10.

FIG. 5 presents a plot of the molecular weight distribution and theshort chain branching distribution of the polymer of Example 5.

FIG. 6 presents a plot of the molecular weight distribution and theshort chain branching distribution of the polymer of Example 6.

FIG. 7 presents a plot of the molecular weight distribution and theshort chain branching distribution of the polymer of Example 11.

FIG. 8 presents a plot of the molecular weight distribution and theshort chain branching distribution of the polymer of Example 12.

FIG. 9 presents a plot of the molecular weight distributions of thepolymers, of Examples 13-16.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. To the extent that any definition or usage provided by anydocument incorporated herein by reference conflicts with the definitionor usage provided herein, the definition or usage provided hereincontrols.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer would be categorized an as ethylene/1-hexenecopolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process would involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

Hydrogen in this disclosure can refer to either hydrogen (H₂) which isused in a polymerization process, or a hydrogen atom (H), which can bepresent, for example, on a metallocene compound. When used to denote ahydrogen atom, hydrogen will be displayed as “H,” whereas if the intentis to disclose the use of hydrogen in a polymerization process, it willsimply be referred to as “hydrogen.”

The term “co-catalyst” is used generally herein to refer toorganoaluminum compounds that can constitute one component of a catalystcomposition. Additionally, “co-catalyst” can refer to other componentsof a catalyst composition including, but not limited to, aluminoxanes,organoboron or organoborate compounds, and ionizing ionic compounds, asdisclosed herein, when used in addition to an activator-support. Theterm “co-catalyst” is used regardless of the actual function of thecompound or any chemical mechanism by which the compound may operate. Inone aspect of this invention, the term “co-catalyst” is used todistinguish that component of the catalyst composition from themetallocene compound(s).

The terms “chemically-treated solid oxide,” “activator-support,”“treated solid oxide compound,” and the like, are used herein toindicate a solid, inorganic oxide of relatively high porosity, which canexhibit Lewis acidic or Brønsted acidic behavior, and which has beentreated with an electron-withdrawing component, typically an anion, andwhich is calcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The terms “support” and“activator-support” are not used to imply these components are inert,and such components should not be construed as an inert component of thecatalyst composition. The activator-support of the present invention canbe a chemically-treated solid oxide. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The term “metallocene,” as used herein, describes a compound comprisingat least one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include H, therefore this inventioncomprises partially saturated ligands such as tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl,partially saturated fluorenyl, substituted partially saturated indenyl,substituted partially saturated fluorenyl, and the like. In somecontexts, the metallocene is referred to simply as the “catalyst,” inmuch the same way the term “co-catalyst” is used herein to refer to, forexample, an organoaluminum compound. Metallocene also is usedgenerically herein to encompass dinuclear metallocene compounds, i.e.,compounds comprising two metallocene moieties linked by a connectinggroup, such as an alkenyl group resulting from an olefin metathesisreaction or a saturated version resulting from hydrogenation orderivatization.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of theclaimed catalyst composition/mixture/system, the nature of the activecatalytic site, or the fate of the co-catalyst, the metallocenecompound(s), any olefin monomer used to prepare a precontacted mixture,or the activator (e.g., activator-support), after combining thesecomponents. Therefore, the terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, encompass the initialstarting components of the composition, as well as whatever product(s)may result from contacting these initial starting components, and thisis inclusive of both heterogeneous and homogenous catalyst systems orcompositions.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which may be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture describes a mixtureof metallocene compound (one or more than one), olefin monomer (ormonomers), and organoaluminum compound (or compounds), before thismixture is contacted with an activator-support(s) and optionaladditional organoaluminum compound. Thus, precontacted describescomponents that are used to contact each other, but prior to contactingthe components in the second, postcontacted mixture. Accordingly, thisinvention may occasionally distinguish between a component used toprepare the precontacted mixture and that component after the mixturehas been prepared. For example, according to this description, it ispossible for the precontacted organoaluminum compound, once it iscontacted with the metallocene compound and the olefin monomer, to havereacted to form at least one different chemical compound, formulation,or structure from the distinct organoaluminum compound used to preparethe precontacted mixture. In this case, the precontacted organoaluminumcompound or component is described as comprising an organoaluminumcompound that was used to prepare the precontacted mixture.

Additionally, the precontacted mixture can describe a mixture ofmetallocene compound(s) and organoaluminum compound(s), prior tocontacting this mixture with an activator-support(s). This precontactedmixture also can describe a mixture of metallocene compound(s), olefinmonomer(s), and activator-support(s), before this mixture is contactedwith an organoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture. Often, the activator-support comprises achemically-treated solid oxide. For instance, the additional componentadded to make up the postcontacted mixture can be a chemically-treatedsolid oxide (one or more than one), and optionally, can include anorgarioaluminum compound which is the same as or different from theorganoaluminum compound used to prepare the precontacted mixture, asdescribed herein. Accordingly, this invention may also occasionallydistinguish between a component used to prepare the postcontactedmixture and that component after the mixture has been prepared.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

For any particular compound disclosed herein, any general or specificstructure presented also encompasses all conformational isomers,regioisomers, and stereoisomers that may arise from a particular set ofsubstituents, unless stated otherwise. Similarly, unless statedotherwise, the general or specific structure also encompasses allenantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, aswould be recognized by a skilled artisan.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of number of atoms, arange of weight ratios, a range of molar ratios, a range of surfaceareas, a range of pore volumes, a range of particle sizes, a range ofcatalyst activities, a range of molecular weights, and so forth. WhenApplicants disclose or claim a range of any type, Applicants' intent isto disclose or claim individually each possible number that such a rangecould reasonably encompass, including end points of the range as well asany sub-ranges and combinations of sub-ranges encompassed therein. Forexample, when the Applicants disclose or claim a chemical moiety havinga certain number of carbon atoms, Applicants' intent is to disclose orclaim individually every possible number that such a range couldencompass, consistent with the disclosure herein. For example, thedisclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group, or inalternative language a hydrocarbyl group having up to 18 carbon atoms,as used herein, refers to a moiety that can be selected independentlyfrom a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range betweenthese two numbers (for example, a C₁ to C_(g) hydrocarbyl group), andalso including any combination of ranges between these two numbers (forexample, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbyl group).

Similarly, another representative example follows for the Mn of anethylene polymer provided in one aspect of this invention. By adisclosure that the Mn of an ethylene polymer can be in a range fromabout 9,000 to about 30,000 g/mol, Applicants intend to recite that theMn can be about 9,000, about 10,000, about 11,000, about 12,000, about13,000, about 14,000, about 15,000, about 16,000, about 17,000, about18,000, about 19,000, about 20,000, about 21,000, about 22,000, about23,000, about 24,000, about 25,000, about 26,000, about 27,000, about28,000, about 29,000, or about 30,000 g/mol. Additionally, the Mn can bewithin any range from about 9,000 to about 30,000 g/mol (for example,from about 10,000 to about 25,000 g/mol), and this also includes anycombination of ranges between about 9,000 and about 30,000 g/mol (forexample, the Mn is in a range from about 9,000 to about 15,000 g/mol, orfrom about 18,000 to about 28,000 g/mol). Likewise, all other rangesdisclosed herein should be interpreted in a manner similar to these twoexamples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps. For example, a catalyst composition of the present invention cancomprise; alternatively, can consist essentially of; or alternatively,can consist of; (i) catalyst component I, (ii) catalyst component II,and (iii) an activator.

The following abbreviations are used in this disclosure:

-   -   Bu—butyl    -   D10—the molecular weight at which 10% of the polymer by weight        has higher molecular weight.    -   D15—the molecular weight at which 15% of the polymer by weight        has higher molecular weight    -   D85—the molecular weight at which 85% of the polymer by weight        has higher molecular weight    -   D90—the molecular weight at which 90% of the polymer by weight        has higher molecular weight    -   Et—ethyl    -   GPC—gel permeation chromatography    -   HLMI—high load melt index    -   M—molecular weight    -   Me—methyl    -   MI—melt index    -   Mn—number average molecular weight    -   Mw—weight-average molecular weight    -   MWD—molecular weight distribution    -   Mz—z-average molecular weight    -   Ph—phenyl    -   Pr—propyl    -   SCB—short chain branches    -   SCBD—short chain branching distribution    -   t-Bu—tert-butyl or t-butyl

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In one aspect, the present invention relates to acatalyst composition, said catalyst composition comprising catalystcomponent I, catalyst component II, and an activator.

In another aspect, an olefin polymerization process is provided and, inthis aspect, the process comprises contacting a catalyst compositionwith an olefin monomer and optionally an olefin comonomer underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises catalyst component I, catalyst componentII, and an activator. In a further aspect, the polymerization processcan be conducted in the absence of added hydrogen.

Olefin homopolymers, copolymers, terpolymers, and the like, can beproduced using the catalyst compositions and methods for olefinpolymerization disclosed herein. For instance, an ethylene polymer ofthe present invention can be characterized as having a broad and/or abimodal molecular weight distribution (MWD); and/or a Mn in a range fromabout 9,000 to about 30,000 g/mol; and/or a ratio of Mw/Mn from about 4to about 20; and/or a ratio of the number of short chain branches (SCB)per 1000 total carbon atoms of the polymer at D90 to the number of SCBper 1000 total carbon atoms of the polymer at D10 in a range from 1.1 toabout 20.

Catalyst Component I

A catalyst composition of the present invention comprises catalystcomponent I, which can comprise:

-   -   a compound having formula (A);    -   a compound having formula (B);    -   a dinuclear compound formed from an alkenyl-substituted compound        having formula (A), formula (B), or a combination thereof; or    -   any combination thereof.        Formula (A) is

wherein:

-   -   M¹ is Zr or Hf;    -   X¹ and X² are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms;    -   E¹ is C or Si;    -   R¹ and R² are independently H, a hydrocarbyl group having up to        18 carbon atoms, or R¹ and R² are connected to form a cyclic or        heterocyclic group having up to 18 carbon atoms; and    -   R³ is H or a hydrocarbyl or hydrocarbylsilyl group having up to        18 carbon atoms.        Formula (B) is

wherein:

-   -   M² is Zr or Hf;    -   X³ is F; Cl; Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or        SO₃R, wherein R is an alkyl or aryl group having up to 18 carbon        atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, or        a hydrocarbylsilyl group, any of which having up to 18 carbon        atoms;    -   E² is C or Si;    -   R⁴ is H or a hydrocarbyl group having up to 18 carbon atoms; and    -   R⁵ is a hydrocarbyl or hydrocarbylsilyl group having up to 18        carbon atoms.

Unless otherwise specified, formulas (A) and (B) above, any otherstructural formulas disclosed herein, and any metallocene speciesdisclosed herein are not designed to show stereochemistry or isomericpositioning of the different moieties (e.g., these formulas are notintended to display cis or trans isomers, or R or S diastereoisomers),although such compounds are contemplated and encompassed by theseformulas and/or structures. Hence, all of the compounds within formula(B) are the meso isomer of such compounds.

Hydrocarbyl is used herein to specify a hydrocarbon radical group thatincludes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl,cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl,and the like, and includes all substituted, unsubstituted, linear,and/or branched derivatives thereof. Unless otherwise specified, thehydrocarbyl groups of this invention typically comprise up to about 18carbon atoms. In another aspect, hydrocarbyl groups can have up to 12carbon atoms, for instance, up to 10 carbon atoms, up to 8 carbon atoms,or up to 6 carbon atoms. A hydrocarbyloxide group, therefore, is usedgenerically to include both alkoxide and aryloxide groups, and thesegroups can comprise up to about 18 carbon atoms. Illustrative andnon-limiting examples of alkoxide and aryloxide groups (i.e.,hydrocarbyloxide groups) include methoxy, ethoxy, propoxy, butoxy,phenoxy, substituted phenoxy, and the like. The term hydrocarbylaminogroup is used generically to refer collectively to alkylamino,arylamino, dialkylamino, and diarylamino groups. Unless otherwisespecified, the hydrocarbylamino groups of this invention comprise up toabout 18 carbon atoms. Hydrocarbylsilyl groups include, but are notlimited to, alkylsilyl groups, alkenylsilyl groups, arylsilyl groups,arylalkylsilyl groups, and the like, which have up to about 18 carbonatoms. For example, illustrative hydrocarbylsilyl groups can includetrimethylsilyl and phenyloctylsilyl. These hydrocarbyloxide,hydrocarbylamino, and hydrocarbylsilyl groups can have up to 12 carbonatoms; alternatively, up to 10 carbon atoms; or alternatively, up to 8carbon atoms, in other aspects of the present invention.

Unless otherwise specified, alkyl groups and alkenyl groups describedherein are intended to include all structural isomers, linear orbranched, of a given moiety; for example, all enantiomers and alldiastereomers are included within this definition. As an example, unlessotherwise specified, the term propyl is meant to include n-propyl andiso-propyl, while the term butyl is meant to include n-butyl, iso-butyl,t-butyl, sec-butyl, and so forth. For instance, non-limiting examples ofoctyl isomers include 2-ethyl hexyl and neooctyl. Suitable examples ofalkyl groups which can be employed in the present invention include, butare not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, and the like. Illustrative examples of alkenylgroups within the scope of the present invention include, but are notlimited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, and the like. The alkenyl group can be aterminal alkenyl group, but this is not a requirement. For instance,specific alkenyl group substituents can include, but are not limited to,3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, 7-octenyl,3-methyl-3-butenyl, 4-methyl-3-pentenyl, 1,1-dimethyl-3-butenyl,1,1-dimethyl-4-pentenyl, and the like.

In this disclosure, aryl is meant to include aryl and arylalkyl groups,and these include, but are not limited to, phenyl, alkyl-substitutedphenyl, naphthyl, alkyl-substituted naphthyl, phenyl-substituted alkyl,naphthyl-substituted alkyl, and the like. Hence, non-limiting examplesof such “aryl” moieties that can be used in the present inventioninclude phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl,phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and thelike. Unless otherwise specified, any substituted aryl moiety usedherein is meant to include all regioisomers; for example, the term tolylis meant to include any possible substituent position, that is, ortho,meta, or para.

In formula (A), M¹ is Zr or Hf and E¹ is C or Si.

X¹ and X² independently can be F; Cl; Br; I; methyl; benzyl; phenyl; H;BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl group; or ahydrocarbyloxide group, a hydrocarbylamino group, or a hydrocarbylsilylgroup. The hydrocarbyloxide group, the hydrocarbylamino group, thehydrocarbylsilyl group and R can have up to 18 carbon atoms or,alternatively, up to 12 carbon atoms.

X¹ and X² independently can be F, Cl, Br, I, benzyl, phenyl, or methyl.For example, X¹ and X² independently are Cl, benzyl, phenyl, or methylin one aspect of this invention. In another aspect, X¹ and X²independently are benzyl, phenyl, or methyl. Yet, in another aspect,both X¹ and X² can be Cl; alternatively, both X¹ and X² can be benzyl;alternatively, both X¹ and X² can be phenyl; or alternatively, both X¹and X² can be methyl.

In formula (A), R¹ and R² are independently H; a hydrocarbyl grouphaving up to 18 carbon atoms or, alternatively, up to 12 carbon atoms;or R¹ and R² are connected to a form a cyclic or heterocyclic grouphaving up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.Cyclic groups include cycloalkyl and cycloalkenyl moieties and suchmoieties can include, but are not limited to, cyclopentyl,cyclopentenyl, cyclohexyl, cyclohexenyl, and the like. For instance,bridging atom E¹, R¹, and R² can form a cyclopentyl or cyclohexylmoiety. Heteroatom-substituted cyclic groups can be formed withnitrogen, oxygen, or sulfur heteroatoms. While these heterocyclic groupscan have up to 12 or 18 carbons atoms, the heterocyclic groups can be3-membered, 4-membered, 5-membered, 6-membered, or 7-membered groups insome aspects of this invention.

In one aspect of the present invention, R¹ and R² are independently H,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, or benzyl. In another aspect, R¹ and R²are the same, and are either methyl, ethyl, propyl, butyl, pentyl, orphenyl. In another aspect, R¹ and R² are independently H or an alkyl ora terminal alkenyl group having up to 8 carbon atoms. In yet anotheraspect, at least one of R¹ and R² is a terminal alkenyl group having upto 8 carbon atoms or, alternatively, up to 6 carbon atoms.

R³ in formula (A) is H or a hydrocarbyl or hydrocarbylsilyl group havingup to 18 carbon atoms. In one aspect, R³ can be hydrocarbyl group havingup to 12 carbon atoms, while in another aspect, R³ can be ahydrocarbylsilyl group having up to 12 carbon atoms (e.g., R³ can betrimethylsilyl). In another aspect, R³ can be H, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl,tolyl, or benzyl. In yet another aspect, R³ is an alkyl or a terminalalkenyl group having up to 8 carbon atoms, or alternatively, up to 6carbon atoms. In still another aspect, R³ is methyl, ethyl, propyl,butyl, pentyl, or hexyl.

It is contemplated in aspects of the invention that X¹ and X²independently can be F, Cl, Br, I, methyl, benzyl, or phenyl in formula(A), while R¹ and R² independently can be H or an hydrocarbyl grouphaving up to 12 carbon atoms, and R³ can be a hydrocarbyl group havingup to 12 carbon atoms. In a further aspect, R¹, R², and R³ independentlycan be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.

Non-limiting examples of ansa-metallocene compounds having formula (A)that are suitable for use in catalyst component I include, but are notlimited to, the following:

and the like, or any combination thereof.

Compounds within formula (B) that are suitable for use in catalystcomponent I are the meso isomer of the respective compounds. In formula(B), M² is Zr or Hf and E² is C or Si.

X³ can be F; Cl; Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R,wherein R is an alkyl or aryl group; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group. Thehydrocarbyloxide group, the hydrocarbylamino group, the hydrocarbylsilylgroup and R can have up to 18 carbon atoms or, alternatively, up to 12carbon atoms.

X³ can be F, Cl, Br, I, benzyl, phenyl, or methyl. For example, X³ isCl, benzyl, phenyl, or methyl in one aspect of this invention. Inanother aspect, X³ is benzyl, phenyl, or methyl. Yet, in another aspect,X³ can be Cl; alternatively, X³ can be benzyl; alternatively, X³ can bephenyl; or alternatively, X³ can be methyl.

In formula (B), R⁴ is H or a hydrocarbyl group having up to 18 carbonatoms or, alternatively, up to 12 carbon atoms. In one aspect of thepresent invention, R⁴ is H, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl.In another aspect, R⁴ is methyl, ethyl, propyl, butyl, pentyl, orphenyl. In yet another aspect, R⁴ is an alkyl group having up to 8carbon atoms.

R⁵ in formula (B) is a hydrocarbyl or hydrocarbylsilyl group having upto 18 carbon atoms. In one aspect, R⁵ can be a hydrocarbyl group havingup to 12 carbon atoms, while in another aspect, R⁵ can be ahydrocarbylsilyl group having up to 12 carbon atoms (e.g., R⁵ can be analkylsilyl, such as trimethylsilyl, or an alkenylsilyl). In anotheraspect, R⁵ can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yetanother aspect, R⁵ is an alkyl or a terminal alkenyl group having up to8 carbon atoms, or alternatively, up to 6 carbon atoms. In still anotheraspect, R⁵ is methyl, ethyl, propyl, butyl, pentyl, hexyl, ethenyl,propenyl, butenyl, pentenyl, or hexenyl; or alternatively, R⁵ is propyl,butyl, propenyl, or butenyl.

In accordance with one aspect of this invention, X³ can be F, Cl, Br, I,methyl, benzyl, or phenyl, while R⁴ can be a hydrocarbyl group having upto 12 carbon atoms, and R⁵ can be a hydrocarbyl group having up to 12carbon atoms. In accordance with another aspect, R⁴ and/or R⁵ can bemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, or benzyl.

Non-limiting examples of ansa-metallocene compounds, in their mesoisomer form, having formula (B) that are suitable for use in catalystcomponent I include, but are not limited to, the following:

and the like, or any combination thereof.

Other representative metallocene compounds which may be employed incatalyst component I in some aspects of this invention are disclosed inU.S. Pat. No. 7,026,494 and U.S. Patent Publication 2009/0088543, thedisclosures of which are incorporated herein by reference in theirentirety.

Catalyst component I also may comprise a dinuclear compound formed froman alkenyl-substituted compound having formula (A), formula (B), or acombination thereof. For example, a dinuclear compound can be formedfrom one alkenyl-substituted compound having formula (A), from onealkenyl-substituted compound having formula (B), from two differentalkenyl-substituted compounds having formula (A), from analkenyl-substituted compound having formula (A) and analkenyl-substituted compound having formula (B), and so forth. Dinuclearmetallocenes are described in U.S. patent application Ser. No.12/489,630 and U.S. Patent Publication Nos. 2009/0170690, 2009/0170691,and 2009/0171041, the disclosures of which are incorporated herein byreference in their entirety.

For instance, dinuclear metallocene compounds can be formed from thefollowing illustrative compounds having formula (A):

The first compound has an alkenyl substituent on the indenyl group andcan be used to form a dinuclear compound as described in U.S. PatentPublication No. 2009/0170691. The second compound has an alkenylsubstituent on the carbon bridging atom and can be used to form adinuclear compound as described in U.S. Patent Publication No.2009/0170690. The first compound and the second compound can be usedtogether to form a heterodinuclear compound as described in U.S. patentapplication Ser. No. 12/489,630.

Catalyst Component II

A catalyst composition of the present invention comprises catalystcomponent II, which can comprise:

-   -   a compound having formula (C);    -   a compound having formula (D);    -   a compound having formula (E);    -   a compound having formula (F);    -   a dinuclear compound formed from an alkenyl-substituted compound        having formula (C), formula (D), formula (E), formula (F), or a        combination thereof; or    -   any combination thereof.        Formula (C) is

wherein:

-   -   M³ is Zr or Hf;    -   X⁴ and X⁵ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms;    -   E³ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >E^(3A)R^(7A)R^(8A),            wherein E^(3A) is C or Si, and R^(7A) and R^(8A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula            —CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B), R^(8B),            R^(7C), and R^(8C) are independently H or a hydrocarbyl            group having up to 10 carbon atoms, or        -   a bridging group having the formula            —SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—, wherein R^(7D), R^(8D),            R^(7E), and R^(8E) are independently H or a hydrocarbyl            group having up to 10 carbon atoms;    -   R⁹ and R¹⁰ are independently H or a hydrocarbyl group having up        to 18 carbon atoms; and    -   Cp¹ is a cyclopentadienyl or indenyl group, any substituent on        Cp¹ is H or a hydrocarbyl or hydrocarbylsilyl group having up to        18 carbon atoms.        Formula (D) is

wherein:

-   -   M⁴ is Zr or Hf;    -   X⁶ and X⁷ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms:    -   E⁴ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >E^(4A)R^(12A)R^(13A),            wherein E^(4A) is C or Si, and R^(12A) and R^(13A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula            —CR^(12B)R^(13B)—CR^(12C)R^(13C)—, wherein R^(12B), R^(13B),            R^(12C), and R^(13C) are independently H or a hydrocarbyl            group having up to 10 carbon atoms, or        -   a bridging group having the formula            —SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, wherein R^(12D),            R^(13D), R^(12E), and R^(13E) are independently H or a            hydrocarbyl group having up to 10 carbon atoms; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are independently H or a hydrocarbyl        group having up to 18 carbon atoms.        Formula (E) is

wherein:

-   -   M⁵ is Zr or Hf;    -   X⁵ and X⁹ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms; and    -   E⁵ is a bridging group selected from:        -   a cyclic or heterocyclic bridging group having up to 18            carbon atoms,        -   a bridging group having the formula >E^(5A)R^(20A)R^(21A),            wherein E^(5A) is C or Si, and R^(20A) and R^(21A) are            independently H or a hydrocarbyl group having up to 18            carbon atoms,        -   a bridging group having the formula —(CH₂)_(n)—, wherein n            is an integer from 2 to 6, inclusive, or        -   a bridging group having the formula            —SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—, wherein R^(20B),            R^(21B), R^(20C), and R^(21C) are independently H or a            hydrocarbyl group having up to 10 carbon atoms.            Formula (F) is

wherein:

-   -   M⁶ is Zr, or Hf;    -   X¹⁰ and X¹¹ are independently F; Cl; Br; I; methyl; benzyl;        phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl        group having up to 18 carbon atoms; or a hydrocarbyloxide group,        a hydrocarbylamino group, or a hydrocarbylsilyl group, any of        which having up to 18 carbon atoms; and    -   Cp² and Cp³ are independently a cyclopentadienyl, indenyl or        fluorenyl group, any substituent on Cp² and Cp³ is independently        H or a hydrocarbyl group having up to 18 carbon atoms.

As noted above, unless otherwise specified, formulas (C), (D), (E), and(F), or any other structural formulas disclosed herein, and anymetallocene species disclosed herein are not designed to showstereochemistry or isomeric positioning of the different moieties (e.g.,these formulas are not intended to display cis or trans isomers, or R orS diastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In formula (C), M³ is Zr or Hf. X⁴ and X⁵ independently can be F; Cl;Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is analkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbylaminogroup, or a hydrocarbylsilyl group. The hydrocarbyloxide group, thehydrocarbylamino group, the hydrocarbylsilyl group and R can have up to18 carbon atoms or, alternatively, up to 12 carbon atoms.

X⁴ and X⁵ independently can be F, Cl, Br, I, benzyl, phenyl, or methyl.For example, X⁴ and X⁵ independently are Cl, benzyl, phenyl, or methylin one aspect of this invention. In another aspect, X⁴ and X⁵independently are benzyl, phenyl, or methyl. Yet, in another aspect,both X⁴ and X⁵ can be Cl; alternatively, both X⁴ and X⁵ can be benzyl;alternatively, both X⁴ and X⁵ can be phenyl; or alternatively, both X⁴and X⁵ can be methyl.

In formula (C), E³ is a bridging group. In accordance with an aspect ofthis invention, E³ can be a cyclic or heterocyclic bridging group havingup to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclicgroups include cycloalkyl and cycloalkenyl moieties and such moietiescan include, but are not limited to, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, and the like. For instance, E³ can be acyclopentyl or cyclohexyl moiety. Heteroatom-substituted cyclic groupscan be formed with nitrogen, oxygen, or sulfur heteroatoms. While theseheterocyclic groups can have up to 12 or 18 carbons atoms, theheterocyclic groups can be 3-membered, 4-membered, 5-membered,6-membered, or 7-membered groups in some aspects of this invention.

In accordance with another aspect of this invention, E³ is a bridginggroup having the formula >E^(3A)R^(7A)R^(8A), wherein E^(3A) is C or Si,and R^(7A) and R^(8A) are independently H or a hydrocarbyl group havingup to 18 carbon atoms or, alternatively, up to 12 carbon atoms. Forinstance, R^(7A) and R^(8A) independently can be H or an alkyl, alkenyl(e.g., a terminal alkenyl), or aryl group having up to 12 carbon atoms.Illustrative non-limiting examples of suitable “aryl” moieties forR^(7A) and/or R^(8A) include phenyl, tolyl, benzyl, dimethylphenyl,trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like. In one aspect, R^(7A) and R^(8A) areindependently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. Inanother aspect, R^(7A) and R^(8A) are the same, and are methyl, ethyl,propyl, butyl, pentyl, or phenyl. In yet another aspect, at least one ofR^(7A) and R^(8A) is phenyl. In still another aspect, at least one ofR^(7A) and R^(8A) is a terminal alkenyl group having up to 6 carbonatoms.

In accordance with another aspect of this invention, E³ is a bridginggroup having the formula —CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B),R^(8B), R^(7C), and R^(8C) are independently H or a hydrocarbyl grouphaving up to 10 carbon atoms or, alternatively, up to 6 carbon atoms.For instance, R^(7B), R^(8B), R^(7C), and R^(8C) independently can be Hor an alkyl or an alkenyl group having up to 6 carbon atoms;alternatively, R^(7B), R^(8B), R^(7C), and R^(8C) independently can beH, methyl, ethyl, propyl, butyl, allyl, butenyl, or pentenyl;alternatively, R^(7B), R^(8B), R^(7C), and R^(8C) independently can beH, methyl, or ethyl; alternatively, R^(7B)R^(8B), R^(7C), and R^(8C) canbe H; or alternatively, R^(7B), R^(8B), R^(7C), and R^(8C) can bemethyl.

In accordance with another aspect of this invention, E³ is a bridginggroup having the formula —SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—, whereinR^(7D), R^(8D), R^(7E), and R^(8E) are independently H or a hydrocarbylgroup having up to 10 carbon atoms or, alternatively, up to 6 carbonatoms. Accordingly, in aspects of this invention, R^(7D), R^(8D),R^(7E), and R^(8E) independently can be H or an alkyl or an alkenylgroup having up to 6 carbon atoms; alternatively, R^(7D), R^(8D),R^(7E), and R^(8E) independently can be H, methyl, ethyl, propyl, butyl,allyl, butenyl, or pentenyl; alternatively, R^(7D), R^(8D), R^(7E), andR^(8E) independently can be H, methyl, or ethyl; alternatively, R^(7D),R^(8D), R^(7E), and R^(8E) can be H; or alternatively, R^(7D), R^(8D),R^(7E), and R^(8E) can be methyl.

R⁹ and R¹⁰ on the fluorenyl group in formula (C) are independently H ora hydrocarbyl group having up to 18 carbon atoms or, alternatively,having up to 12 carbon atoms. Accordingly, R⁹ and R¹⁰ independently canbe H or a hydrocarbyl group having up to 8 carbon atoms, such as, forexample, alkyl groups: methyl, ethyl, propyl, butyl, pentyl, or hexyl,and the like. In some aspects, R⁹ and R¹⁰ are independently methyl,ethyl, propyl, n-butyl, t-butyl, or hexyl, while in other aspects, R⁹and R¹⁰ are independently H or t-butyl. For example, both R⁹ and R¹⁰ canbe H or, alternatively, both R⁹ and R¹⁰ can be t-butyl.

In formula (C), Cp¹ is a cyclopentadienyl or indenyl. Often, Cp¹ is acyclopentadienyl group. Any substituent on Cp¹ can be H or a hydrocarbylor hydrocarbylsilyl group having up to 18 carbon atoms; oralternatively, any substituent can be H or a hydrocarbyl orhydrocarbylsilyl group having up to 12 carbon atoms. Possiblesubstituents on Cp¹ may include H, therefore this invention comprisespartially saturated ligands such as tetrahydroindenyl, partiallysaturated indenyl, and the like.

In one aspect, Cp¹ has no additional substitutions other than thoseshown in formula (C), e.g., no substituents other than the bridginggroup E³. In another aspect, Cp¹ can have one or two substituents, andeach substituent independently is H or an alkyl, alkenyl, alkylsilyl, oralkenylsilyl group having up to 8 carbon atoms, or alternatively, up to6 carbon atoms. Yet, in another aspect, Cp¹ can have a single H, methylethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, or octenyl substituent.

In accordance with one aspect of this invention, X⁴ and X⁵ independentlycan be F, Cl, Br, I, benzyl, phenyl, or methyl, while R⁹ and R¹⁰independently can be H or t-butyl, and Cp¹ either has no additionalsubstituents or Cp¹ can have a single substituent selected from H or analkyl, alkenyl, alkylsilyl, or alkenylsilyl group having up to 8 carbonatoms. In these and other aspects, E³ can be cyclopentyl or cyclohexyl;alternatively, E³ can be a bridging group having the formula>E^(3A)R^(7A)R^(8A), wherein E^(3A) is C or Si, and R^(7A) and R^(8A)are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl;alternatively, E³ can be a bridging group having the formula—CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B), R^(8B), R^(7C), andR^(8C) are independently H or methyl; or alternatively, E³ can be abridging group having the formula —SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—,wherein R^(7D), R^(8D), R^(7E), and R^(8E) are independently H ormethyl.

Non-limiting examples of ansa-metallocene compounds having formula (C)that are suitable for use in catalyst component II include, but are notlimited to, the following:

and the like, or any combination thereof.

In formula (D), M⁴ is Zr or Hf. X⁶ and X⁷ independently can be F; Cl;Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is analkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbylaminogroup, or a hydrocarbylsilyl group. The hydrocarbyloxide group, thehydrocarbylamino group, the hydrocarbylsilyl group and R can have up to18 carbon atoms or, alternatively, up to 12 carbon atoms.

X⁶ and X⁷ independently can be F, Cl, Br, I, benzyl, phenyl, or methyl.For example, X⁶ and X⁷ independently are Cl, benzyl, phenyl, or methylin one aspect of this invention. In another aspect, X⁶ and X⁷independently are benzyl, phenyl, or methyl. Yet, in another aspect,both X⁶ and X⁷ can be Cl; alternatively, both X⁶ and X⁷ can be benzyl;alternatively, both X⁶ and X⁷ can be phenyl; or alternatively, both X⁶and X⁷ can be methyl.

In formula (D), E⁴ is a bridging group. In accordance with an aspect ofthis invention, E⁴ can be a cyclic or heterocyclic bridging group havingup to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclicgroups include cycloalkyl and cycloalkenyl moieties and such moietiescan include, but are not limited to, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, and the like. For instance, E⁴ can be acyclopentyl or cyclohexyl moiety. Heteroatom-substituted cyclic groupscan be formed with nitrogen, oxygen, or sulfur heteroatoms. While theseheterocyclic groups can have up to 12 or 18 carbons atoms, theheterocyclic groups can be 3-membered, 4-membered, 5-membered,6-membered, or 7-membered groups in some aspects of this invention.

In accordance with another aspect of this invention, E⁴ is a bridginggroup having the formula >E^(4A)R^(12A)R^(13A), wherein E^(4A) is C orSi, and R^(12A) and R^(13A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.For instance, R^(12A) and R^(13A) independently can be H or an alkyl,alkenyl (e.g., a terminal alkenyl), or aryl group having up to 12 carbonatoms. Illustrative non-limiting examples of suitable “aryl” moietiesfor R^(12A) and/or R^(13A) include phenyl, tolyl, benzyl,dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like. In one aspect, R^(12A) and R^(13A)independently can be an alkyl, a terminal alkenyl, or aryl group havingup to 10 carbon atoms. In another aspect, R^(12A) and R^(13A) areindependently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yetanother aspect, R^(12A) and R^(13A) are the same, and are methyl, ethyl,propyl, butyl, pentyl, or phenyl. In still another aspect, at least oneof R^(12A) and R^(13A) is phenyl and/or at least one of R^(12A) andR^(13A) is a terminal alkenyl group having up to 8 carbon atoms.

In accordance with another aspect of this invention, E⁴ is a bridginggroup having the formula —CR^(12B)R^(13B)—CR^(12C)R^(13C)—, whereinR^(12B), R^(13B), R^(12C), and R^(13C) are independently H or ahydrocarbyl group having up to 10 carbon atoms or, alternatively, up to6 carbon atoms. For instance, R^(12B), R^(13B), R^(12C), and R^(13C)independently can be H or an alkyl or an alkenyl group having up to 6carbon atoms; alternatively, R^(12B), R^(13B), R^(12C), and R^(13C)independently can be H, methyl, ethyl, propyl, butyl, allyl, butenyl, orpentenyl; alternatively, R^(12B), R^(13B), R^(12C), and R^(13C)independently can be H, methyl, ethyl, propyl, or butyl; alternatively,R^(12B), R^(13B), R^(12C), and R^(13C) independently can be H, methyl,or ethyl; alternatively, R^(12B), R^(13B), R^(12C), and R^(13C) can beH; or alternatively, R^(12B), R^(13B), R^(12C), and R^(13C) can bemethyl.

In accordance with another aspect of this invention, E⁴ is a bridginggroup having the formula —SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, whereinR^(12D), R^(13D), R^(12E), and R^(13E) are independently H or ahydrocarbyl group having up to 10 carbon atoms or, alternatively, up to6 carbon atoms. Accordingly, in aspects of this invention, R^(12D),R^(13D), R^(12E), and R^(13E) independently can be H or an alkyl or analkenyl group having up to 6 carbon atoms; alternatively, R^(12D),R^(13D), R^(12E), and R^(13E) independently can be H, methyl, ethyl,propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R^(12D),R^(13D), R^(12E), and R^(13E) independently can be H, methyl, ethyl,propyl, or butyl; alternatively, R^(12D), R^(13D), R^(12E), and R^(13E)independently can be H, methyl, or ethyl; alternatively, R^(12D),R^(13D), R^(12E), and R^(13E) can be H; or alternatively, R^(12D),R^(13D), R^(12E), and R^(13E) can be methyl.

R¹⁴, R¹⁵, R¹⁶, and R¹⁷ on the fluorenyl groups in formula (D) areindependently H or a hydrocarbyl group having up to 18 carbon atoms or,alternatively, having up to 12 carbon atoms. Accordingly, R¹⁴, R¹⁵, R¹⁶,and R¹⁷ independently can be H or a hydrocarbyl group having up to 8carbon atoms, such as, for example, alkyl groups: methyl, ethyl, propyl,butyl, pentyl, or hexyl, and the like. In some aspects, R¹⁴, R¹⁵, R¹⁶,and R⁷ are independently methyl, ethyl, propyl, n-butyl, t-butyl, orhexyl, while in other aspects, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are independentlyH or t-butyl. For example, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can be H or,alternatively, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can be t-butyl.

It is contemplated that X⁶ and X⁷ independently can be F, Cl, Br, I,benzyl, phenyl, or methyl in formula (D), and R¹⁴, R¹⁵, R¹⁶, and R¹⁷independently can be H or t-butyl. In these and other aspects, E⁴ can becyclopentyl or cyclohexyl; alternatively, E⁴ can be a bridging grouphaving the formula >E^(4A)R^(12A)R^(13A), wherein E^(4A) is C or Si, andR^(12A) and R^(13A) are independently H, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl,or benzyl; alternatively, E⁴ can be a bridging group having the formula—CR^(12B)R^(13B)—CR^(12C)R^(13C)—, wherein R^(12B), R^(13B), R^(12C),and R^(13C) are independently H or methyl; or alternatively, E⁴ can be abridging group having the formula —SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—,wherein R^(12D), R^(13D), R^(12E), and R^(13E) are independently H ormethyl.

Non-limiting examples of ansa-metallocene compounds having formula (D)that are suitable for use in catalyst component II include, but are notlimited to, the following:

and the like, or any combination thereof.

In formula (E), M⁵ is Zr or Hf. X⁸ and X⁹ independently can be F; Cl;Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is analkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbylaminogroup, or a hydrocarbylsilyl group. The hydrocarbyloxide group, thehydrocarbylamino group, the hydrocarbylsilyl group and R can have up to18 carbon atoms or, alternatively, up to 12 carbon atoms.

X⁸ and X⁹ independently can be F, Cl, Br, I, benzyl, phenyl, or methyl.For example, X⁸ and X⁹ independently are Cl, benzyl, phenyl, or methylin one aspect of this invention. In another aspect, X⁸ and X⁹independently are benzyl, phenyl, or methyl. Yet, in another aspect,both X⁸ and X⁹ can be Cl; alternatively, both X⁸ and X⁹ can be benzyl;alternatively, both X⁸ and X⁹ can be phenyl; or alternatively, both X⁸and X⁹ can be methyl.

In formula (E), E⁵ is a bridging group. In accordance with an aspect ofthis invention, E⁵ can be a cyclic or heterocyclic bridging group havingup to 18 carbon atoms, or alternatively, up to 12 carbon atoms. Cyclicgroups include cycloalkyl and cycloalkenyl moieties and such moietiescan include, but are not limited to, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, and the like. For instance, E⁵ can be acyclopentyl or cyclohexyl moiety. Heteroatom-substituted cyclic groupscan be formed with nitrogen, oxygen, or sulfur heteroatoms. While theseheterocyclic groups can have up to 12 or 18 carbons atoms, theheterocyclic groups can be 3-membered, 4-membered, 5-membered,6-membered, or 7-membered groups in some aspects of this invention.

In accordance with another aspect of this invention, E⁵ is a bridginggroup having the formula >E^(5A)R^(20A)R^(21A), wherein E^(5A) is C orSi, and R^(20A) and R^(21A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms or, alternatively, up to 12 carbon atoms.For instance, R^(20A) and R^(21A) independently can be H or an alkyl,alkenyl (e.g., a terminal alkenyl), or aryl group having up to 12 carbonatoms. Illustrative non-limiting examples of suitable “aryl” moietiesfor R^(20A) and/or R^(21A) include phenyl, tolyl, benzyl,dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl,propyl-2-phenylethyl, and the like. In one aspect, R^(20A) and R^(21A)independently can be an alkyl, a terminal alkenyl, or aryl group havingup to 10 carbon atoms. In another aspect, R^(20A) and R^(21A) areindependently H, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl. In yetanother aspect, R^(20A) and R^(21A) are the same, and are methyl, ethyl,propyl, butyl, pentyl, or phenyl. In still another aspect, at least oneof R^(20A) and R^(21A) is phenyl and/or at least one of R^(20A) andR^(21A) is a terminal alkenyl group having up to 8 carbon atoms.

In accordance with another aspect of this invention, E⁵ is a bridginggroup having the formula —(CH₂)_(n)—, wherein n is an integer from 2 to6, inclusive. The integer n can be 2, 3, or 4 in some aspects of thisinvention.

In accordance with another aspect of this invention, E⁵ is a bridginggroup having the formula —SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—, whereinR^(20B), R^(21B), R^(20C), and R^(21C) are independently H or ahydrocarbyl group having up to 10 carbon atoms or, alternatively, up to6 carbon atoms. Accordingly, in aspects of this invention, R^(20B),R^(21B), R^(20C), and R^(21C) independently can be H or an alkyl or analkenyl group having up to 6 carbon atoms; alternatively, R^(20B),R^(21B), R^(20C), and R^(21C) independently can be H, methyl, ethyl,propyl, butyl, allyl, butenyl, or pentenyl; alternatively, R^(20B),R^(21B), R^(20C), and R^(21C) independently can be H, methyl, ethyl,propyl, or butyl; alternatively, R^(20B), R^(21B), R^(20C), and R^(21C)independently can be H, methyl, or ethyl; alternatively, R^(20B),R^(21B), R^(20C), and R^(21C) can be H; or alternatively, R^(20B),R^(21B), R^(20C), and R^(21C) can be methyl.

In an aspect of this invention, X⁸ and X⁹ in formula (E) independentlycan be F, Cl, Br, I, benzyl, phenyl, or methyl, and in some aspects, E⁵can be cyclopentyl or cyclohexyl; alternatively, E⁵ can be a bridginggroup having the formula >E^(5A)R^(20A)R^(21A), wherein E^(5A) is C orSi, and R^(20A) and R^(21A) are independently H, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl,tolyl, or benzyl; alternatively, E⁵ can be a bridging group having theformula —(CH₂)_(n)—, wherein n is equal to 2, 3, or 4; or alternatively,E⁵ can be a bridging group having the formula—SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—, wherein R^(20B), R^(21B), R^(20C),and R^(21C) are independently H or methyl.

Non-limiting examples of ansa-metallocene compounds having formula (E)that are suitable for use in catalyst component II include, but are notlimited to, the following:

and the like, or any combination thereof.

In formula (F), M⁶ is Zr or Hf. X¹⁰ and X¹¹ independently can be F; Cl;Br; I; methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is analkyl or aryl group; or a hydrocarbyloxide group, a hydrocarbylaminogroup, or a hydrocarbylsilyl group. The hydrocarbyloxide group, thehydrocarbylamino group, the hydrocarbylsilyl group and R can have up to18 carbon atoms or, alternatively, up to 12 carbon atoms.

X¹⁰ and X¹¹ independently can be F, Cl, Br, I, benzyl, phenyl, ormethyl. For example, X¹⁰ and X¹¹ independently are Cl, benzyl, phenyl,or methyl in one aspect of this invention. In another aspect, X¹⁰ andX¹¹ independently are benzyl, phenyl, or methyl. Yet, in another aspect,both X¹⁰ and X¹¹ can be Cl; alternatively, both X¹⁰ and X¹¹ can bebenzyl; alternatively, both X¹⁰ and X¹¹ can be phenyl; or alternatively,both X¹⁰ and X¹¹ can be methyl.

In formula (F), Cp² and Cp³ are independently a cyclopentadienyl,indenyl or fluorenyl group. Often, Cp² and Cp³ are independently acyclopentadienyl or indenyl group. Any substituent on Cp² and Cp³independently can be H or a hydrocarbyl group having up to 18 carbonatoms, or alternatively, any substituent can be H or a hydrocarbyl grouphaving up to 12 carbon atoms. Possible substituents on Cp² and Cp³ mayinclude H, therefore this invention comprises partially saturatedligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, and the like.

In one aspect, Cp² and Cp³ have no substitutions other than those shownin formula (F), e.g., Cp² and Cp³ independently can be an unsubstitutedcyclopentadienyl or unsubstituted indenyl. In another aspect, Cp² and/orCp³ can have one or two substituents, and each substituent independentlycan be H or a hydrocarbyl group having up to 10 carbon atoms, such as,for example, an alkyl, alkenyl, or aryl group. Yet, in another aspect,Cp² and/or Cp³ can have one or two substituents, and each substituentindependently can be H, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, phenyl, tolyl, or benzyl, while in other aspects, eachsubstituent independently can be methyl, ethyl, propyl, butyl, ethenyl,propenyl, butenyl, or pentenyl.

In some aspects of this invention, X¹⁰ and X¹¹ independently can be F,Cl, Br, I, benzyl, phenyl, or methyl, while Cp² and Cp³ areindependently an unsubstituted cyclopentadienyl or unsubstituted indenylgroup. Alternatively, Cp² and Cp³ independently may be substituted withone or two substituents, and these substituents independently can be Hor a hydrocarbyl group having up to 10 carbon atoms, such as, forexample, methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,phenyl, tolyl, or benzyl.

Non-limiting examples of unbridged metallocene compounds having formula(F) that are suitable for use in catalyst component II include, but arenot limited to, the following:

and the like, or any combination thereof.

Other representative metallocene compounds which may be employed incatalyst component II in some aspects of this invention are disclosed inU.S. Pat. Nos. 7,199,073, 7,312,283, 7,456,243, and 7,521,572, thedisclosures of which are incorporated herein by reference in theirentirety.

Catalyst component II also may comprise a dinuclear compound formed froman alkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof.

For example, a dinuclear compound can be formed from onealkenyl-substituted compound having formula (C), from onealkenyl-substituted compound having formula (D), from two differentalkenyl-substituted compounds having formula (E), from analkenyl-substituted compound having formula (C) and analkenyl-substituted compound having formula (E), and so forth. Dinuclearmetallocenes are described in U.S. patent application Ser. No.12/489,630 and U.S. Patent Publication Nos. 2009/0170690, 2009/0170691,and 2009/0171041, the disclosures of which are incorporated herein byreference in their entirety.

For instance, dinuclear metallocene compounds can be formed from thefollowing illustrative metallocene compounds having formula (C), formula(D), formula (E), and formula (F), respectively:

The metallocene compound having formula (C) has an alkenyl substituenton the cyclopentadienyl group and can be used to form a dinuclearcompound as described in U.S. Patent Publication No. 2009/0170691. Themetallocene compounds having formula (D) and formula (E) have an alkenylsubstituent on the silicon bridging atom and can be used to form adinuclear compound as described in U.S. Patent Publication No.2009/0170690. The unbridged metallocene compound having formula (F) hasan alkenyl substituent on the indenyl group and can be used to form adinuclear compound as described in U.S. Patent Publication No.2009/0171041. Additionally, any two of these metallocene compounds withalkenyl substituents having formula (C), formula (D), formula (E), orformula (F) can be used together to form a heterodinuclear compound asdescribed in U.S. patent application Ser. No. 12/489,630.

Activator-Support

The present invention encompasses various catalyst compositionscontaining an activator, which can be an activator-support. In oneaspect, the activator-support comprises a chemically-treated solidoxide. Alternatively, the activator-support can comprise a clay mineral,a pillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or any combination thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While thechemically-treated solid oxide activates the metallocene in the absenceof co-catalysts, it is not necessary to eliminate co-catalysts from thecatalyst composition. The activation function of the activator-supportis evident in the enhanced activity of catalyst composition as a whole,as compared to a catalyst composition containing the correspondinguntreated solid oxide. However, it is believed that thechemically-treated solid oxide can function as an activator, even in theabsence of an organoaluminum compound, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials is by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention are formed generallyfrom an inorganic solid oxide that exhibits Lewis acidic or Brønstedacidic behavior and has a relatively high porosity. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide has a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide has a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide has a surface area of from about 100to about 1000 m²/g. In yet another aspect, the solid oxide has a surfacearea of from about 200 to about 800 m²/g. In still another aspect of thepresent invention, the solid oxide has a surface area of from about 250to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed., Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide include, but are not limitedto, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, CO₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃,La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxides thereof, andcombinations thereof. For example, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, mixed oxides thereof, or any combination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide compound. Examplesof mixed oxides that can be used in the activator-support of the presentinvention include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, various clay minerals,alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria,silica-boria, aluminophosphate-silica, titania-zirconia, and the like.The solid oxide of this invention also encompasses oxide materials suchas silica-coated alumina, as described in U.S. Patent Publication No.2010-0076167, the disclosure of which is incorporated herein byreference in its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present invention. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this invention. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or any combination thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions of the present invention canbe, or can comprise, fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In some aspects, the activator-support comprises fluorided alumina;alternatively, comprises chlorided alumina; alternatively, comprisessulfated alumina; alternatively, comprises fluorided silica-alumina;alternatively, comprises sulfated silica-alumina; alternatively,comprises fluorided silica-zirconia; alternatively, comprises chloridedsilica-zirconia; or alternatively, comprises fluorided silica-coatedalumina.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention is employing two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, one example of such a process by which a chemically-treated solidoxide is prepared is as follows: a selected solid oxide, or combinationof solid oxides, is contacted with a first electron-withdrawing anionsource compound to form a first mixture; this first mixture is calcinedand then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture; the second mixture is then calcinedto form a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide comprises a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof. Any method of impregnating the solid oxide materialwith a metal can be used.

The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound isadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc is often used to impregnate the solid oxidebecause it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion is typically calcined. Alternatively, a solidoxide material, an electron-withdrawing anion source, and the metal saltor metal-containing compound are contacted and calcined simultaneously.

Various processes are used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. The contact product typically is calcined either during orafter the solid oxide is contacted with the electron-withdrawing anionsource. The solid oxide can be calcined or uncalcined. Various processesto prepare solid oxide activator-supports that can be employed in thisinvention have been reported. For example, such methods are described inU.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553,6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987,6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, and6,750,302, the disclosures of which are incorporated herein by referencein their entirety.

According to one aspect of the present invention, the solid oxidematerial is chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally is chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present invention, the solid oxide material andelectron-withdrawing anion source are contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, is calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

-   -   1) contacting a solid oxide (or solid oxides) with an        electron-withdrawing anion source compound (or compounds) to        form a first mixture; and    -   2) calcining the first mixture to form the solid oxide        activator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) is produced by aprocess comprising:

-   -   1) contacting a solid oxide (or solid oxides) with a first        electron-withdrawing anion source compound to form a first        mixture;    -   2) calcining the first mixture to produce a calcined first        mixture;    -   3) contacting the calcined first mixture with a second        electron-withdrawing anion source compound to form a second        mixture; and    -   4) calcining the second mixture to form the solid oxide        activator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide is produced or formed by contacting thesolid oxide with the electron-withdrawing anion source compound, wherethe solid oxide compound is calcined before, during, or after contactingthe electron-withdrawing anion source, and where there is a substantialabsence of aluminoxanes, organoboron or organoborate compounds, andionizing ionic compounds.

Calcining of the treated solid oxide generally is conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining is conducted in an oxidizing atmosphere,such as air. Alternatively, an inert atmosphere, such as nitrogen orargon, or a reducing atmosphere, such as hydrogen or carbon monoxide,can be used.

According to one aspect of the present invention, the solid oxidematerial is treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofchloride ion (termed a “chloriding agent”), a source of fluoride ion(termed a “fluoriding agent”), or a combination thereof, and calcined toprovide the solid oxide activator. Useful acidic activator-supportsinclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated witha metal ion.

The chemically-treated solid oxide can comprise a fluorided solid oxidein the form of a particulate solid. The fluorided solid oxide can beformed by contacting a solid oxide with a fluoriding agent. The fluorideion can be added to the oxide by forming a slurry of the oxide in asuitable solvent such as alcohol or water including, but not limited to,the one to three carbon alcohols because of their volatility and lowsurface tension. Examples of suitable fluoriding agents include, but arenot limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄PF₆), hexafluorotitanic acid (H₂TiF₆), ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆),AlF₃, NH₄AlF₄, analogs thereof, and combinations thereof. Triflic acidand ammonium triflate also can be employed. For example, ammoniumbifluoride (NH₄HF₂) can be used as the fluoriding agent, due to its easeof use and availability.

If desired, the solid oxide is treated with a fluoriding agent duringthe calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the inventioninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent is to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide is formed by contacting asolid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentis to vaporize a chloriding agent into a gas stream used to fluidize thesolid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally is from about 1 to about 50% by weight, where theweight percent is based on the weight of the solid oxide, for example,silica-alumina, before calcining. According to another aspect of thisinvention, the amount of fluoride or chloride ion present beforecalcining the solid oxide is from about 1 to about 25% by weight, andaccording to another aspect of this invention, from about 2 to about 20%by weight. According to yet another aspect of this invention, the amountof fluoride or chloride ion present before calcining the solid oxide isfrom about 4 to about 10% by weight. Once impregnated with halide, thehalided oxide can be dried by any suitable method including, but notlimited to, suction filtration followed by evaporation, drying undervacuum, spray drying, and the like, although it is also possible toinitiate the calcining step immediately without drying the impregnatedsolid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallyhas a pore volume greater than about 0.5 cc/g. According to one aspectof the present invention, the pore volume is greater than about 0.8cc/g, and according to another aspect of the present invention, greaterthan about 1.0 cc/g. Further, the silica-alumina generally has a surfacearea greater than about 100 m²/g. According to another aspect of thisinvention, the surface area is greater than about 250 m²/g. Yet, inanother aspect, the surface area is greater than about 350 m²/g.

The silica-alumina utilized in the present invention typically has analumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina isfrom about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component comprises alumina withoutsilica, and according to another aspect of this invention, the solidoxide component comprises silica without alumina.

The sulfated solid oxide comprises sulfate and a solid oxide component,such as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is treated further with a metal ion suchthat the calcined sulfated oxide comprises a metal. According to oneaspect of the present invention, the sulfated solid oxide comprisessulfate and alumina. In some instances, the sulfated alumina is formedby a process wherein the alumina is treated with a sulfate source, forexample, sulfuric acid or a sulfate salt such as ammonium sulfate. Thisprocess is generally performed by forming a slurry of the alumina in asuitable solvent, such as alcohol or water, in which the desiredconcentration of the sulfating agent has been added. Suitable organicsolvents include, but are not limited to, the one to three carbonalcohols because of their volatility and low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining is from about 0.5 to about 100 parts by weightsulfate ion to about 100 parts by weight solid oxide. According toanother aspect of this invention, the amount of sulfate ion presentbefore calcining is from about 1 to about 50 parts by weight sulfate ionto about 100 parts by weight solid oxide, and according to still anotheraspect of this invention, from about 5 to about 30 parts by weightsulfate ion to about 100 parts by weight solid oxide. These weightratios are based on the weight of the solid oxide before calcining. Onceimpregnated with sulfate, the sulfated oxide can be dried by anysuitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention comprises an ion-exchangeable activator-support, including butnot limited to silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays are used as activator-supports.When the acidic activator-support comprises an ion-exchangeableactivator-support, it can optionally be treated with at least oneelectron-withdrawing anion such as those disclosed herein, thoughtypically the ion-exchangeable activator-support is not treated with anelectron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention comprises clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather is to beconsidered an active part of the catalyst composition, because of itsintimate association with the metallocene component.

According to another aspect of the present invention, the clay materialsof this invention encompass materials either in their natural state orthat have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention comprises clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention alsoencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(In), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support comprises a pillared clay. The term “pillared clay” isused to refer to clay materials that have been ion exchanged with large,typically polynuclear, highly charged metal complex cations. Examples ofsuch ions include, but are not limited to, Keggin ions which can havecharges such as 7+, various polyoxometallates, and other large ions.Thus, the term pillaring refers to a simple exchange reaction in whichthe exchangeable cations of a clay material are replaced with large,highly charged ions, such as Keggin ions. These polymeric cations arethen immobilized within the interlayers of the clay and when calcinedare converted to metal oxide “pillars,” effectively supporting the claylayers as column-like structures. Thus, once the clay is dried andcalcined to produce the supporting pillars between clay layers, theexpanded lattice structure is maintained and the porosity is enhanced.The resulting pores can vary in shape and size as a function of thepillaring material and the parent clay material used. Examples ofpillaring and pillared clays are found in: T. J. Pinnavaia, Science 220(4595), 365-371 (1983); J. M. Thomas, Intercalation Chemistry, (S.Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press,Inc., (1972); U.S. Pat. No. 4,452,910; U.S. Pat. No. 5,376,611; and U.S.Pat. No. 4,060,480; the disclosures of which are incorporated herein byreference in their entirety.

The pillaring process utilizes clay minerals having exchangeable cationsand layers capable of expanding. Any pillared clay that can enhance thepolymerization of olefins in the catalyst composition of the presentinvention can be used. Therefore, suitable clay minerals for pillaringinclude, but are not limited to, allophanes; smectites, bothdioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof suchas montmorillonites (bentonites), nontronites, hectorites, or laponites;halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layerclays; the fibrous clays including but not limited to sepiolites,attapulgites, and palygorskites; a serpentine clay; illite; laponite;saponite; and any combination thereof. In one aspect, the pillared clayactivator-support comprises bentonite or montmorillonite. The principalcomponent of bentonite is montmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite is pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that are used include, but are not limited to, silica,silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria,aluminophosphate, aluminum phosphate, silica-titania, coprecipitatedsilica/titania, mixtures thereof, or any combination thereof.

According to another aspect of the present invention, one or more of themetallocene compounds can be precontacted with an olefin monomer and anorganoaluminum compound for a first period of time prior to contactingthis mixture with the activator-support. Once the precontacted mixtureof the metallocene compound(s), olefin monomer, and organoaluminumcompound is contacted with the activator-support, the compositionfurther comprising the activator-support is termed a “postcontacted”mixture. The postcontacted mixture can be allowed to remain in furthercontact for a second period of time prior to being charged into thereactor in which the polymerization process will be carried out.

According to yet another aspect of the present invention, one or more ofthe metallocene compounds can be precontacted with an olefin monomer andan activator-support for a first period of time prior to contacting thismixture with the organoaluminum compound. Once the precontacted mixtureof the metallocene compound(s), olefin monomer, and activator-support iscontacted with the organoaluminum compound, the composition furthercomprising the organoaluminum is termed a “postcontacted” mixture. Thepostcontacted mixture can be allowed to remain in further contact for asecond period of time prior to being introduced into the polymerizationreactor.

Organoaluminum Compounds

In some aspects, catalyst compositions of the present invention cancomprise one or more organoaluminum compounds. Such compounds caninclude, but are not limited to, compounds having the formula:(R^(C))₃Al;where R^(C) is an aliphatic group having from 1 to 10 carbon atoms. Forexample, R^(C) can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:Al(X^(A))_(m)(X^(B))_(3−m),where X^(A) is a hydrocarbyl; X^(B) is an alkoxide or an aryloxide, ahalide, or a hydride; and m is from 1 to 3, inclusive. Hydrocarbyl isused herein to specify a hydrocarbon radical group and includes, but isnot limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like,and includes all substituted, unsubstituted, branched, linear, and/orheteroatom substituted derivatives thereof.

In one aspect, X^(A) is a hydrocarbyl having from 1 to about 18 carbonatoms. In another aspect of the present invention, X^(A) is an alkylhaving from 1 to 10 carbon atoms. For example, X^(A) can be methyl,ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, inyet another aspect of the present invention.

According to one aspect of the present invention, X^(B) is an alkoxideor an aryloxide, any one of which has from 1 to 18 carbon atoms, ahalide, or a hydride. In another aspect of the present invention, X^(B)is selected independently from fluorine and chlorine. Yet, in anotheraspect, X^(B) is chlorine.

In the formula, Al(X^(A))_(m)(X^(B))_(3−m), m is a number from 1 to 3,inclusive, and typically, m is 3. The value of m is not restricted to bean integer; therefore, this formula includes sesquihalide compounds orother organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention include, but are not limited to, trialkylaluminumcompounds, dialkylaluminum halide compounds, dialkylaluminum alkoxidecompounds, dialkylaluminum hydride compounds, and combinations thereof.Specific non-limiting examples of suitable organoaluminum compoundsinclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof.

The present invention contemplates a method of precontacting ametallocene compound with an organoaluminum compound and an olefinmonomer to form a precontacted mixture, prior to contacting thisprecontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound is added to the precontacted mixture and another portion of theorganoaluminum compound is added to the postcontacted mixture preparedwhen the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components arecontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

The present invention further provides a catalyst composition which cancomprise an aluminoxane compound. As used herein, the term “aluminoxane”refers to aluminoxane compounds, compositions, mixtures, or discretespecies, regardless of how such aluminoxanes are prepared, formed orotherwise provided. For example, a catalyst composition comprising analuminoxane compound can be prepared in which aluminoxane is provided asthe poly(hydrocarbyl aluminum oxide), or in which aluminoxane isprovided as the combination of an aluminum alkyl compound and a sourceof active protons such as water. Aluminoxanes are also referred to aspoly(hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components typically are contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner is collected by any suitable method, for example,by filtration. Alternatively, the catalyst composition is introducedinto the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein R in this formula is a linear or branched alkyl having from 1 to10 carbon atoms, and p is an integer from 3 to 20, are encompassed bythis invention. The AlRO moiety shown here also constitutes therepeating unit in a linear aluminoxane. Thus, linear aluminoxanes havingthe formula:

wherein R in this formula is a linear or branched alkyl having from 1 to10 carbon atoms, and q is an integer from 1 to 50, are also encompassedby this invention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein R^(t) is a terminal linear orbranched alkyl group having from 1 to 10 carbon atoms; R^(b) is abridging linear or branched alkyl group having from 1 to 10 carbonatoms; r is 3 or 4; and α is equal to n_(Al(3))−n_(O(2))+n_(O(4)),wherein n_(Al(3)) is the number of three coordinate aluminum atoms,n_(O(2)) is the number of two coordinate oxygen atoms, and n_(O(4)) isthe number of 4 coordinate oxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention are represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, the Rgroup is typically a linear or branched C₁-C₆ alkyl, such as methyl,ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,isopentylaluminoxane, neopentylaluminoxane, and the like, or anycombination thereof. Methylaluminoxane, ethylaluminoxane, andiso-butylaluminoxane are prepared from trimethylaluminum,triethylaluminum, or triisobutylaluminum, respectively, and sometimesare referred to as poly(methyl aluminum oxide), poly(ethyl aluminumoxide), and poly(isobutyl aluminum oxide), respectively. It is alsowithin the scope of the invention to use an aluminoxane in combinationwith a trialkylaluminum, such as that disclosed in U.S. Pat. No.4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q are at least 3. However, depending upon how theorganoaluminoxane is prepared, stored, and used, the value of p and qcan vary within a single sample of aluminoxane, and such combinations oforganoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of metallocene compound(s) in thecomposition is generally between about 1:10 and about 100,000:1. Inanother aspect, the molar ratio is in a range from about 5:1 to about15,000:1. Optionally, aluminoxane can be added to a polymerization zonein ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/Lto about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as(R^(C))₃Al, to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic R—Al—Oaluminoxane species, both of which are encompassed by this invention.Alternatively, organoaluminoxanes are prepared by reacting an aluminumalkyl compound, such as (R^(C))₃Al, with a hydrated salt, such ashydrated copper sulfate, in an inert organic solvent.

Organoboron/Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate compound. Suchcompounds include neutral boron compounds, borate salts, and the like,or combinations thereof. For example, fluoroorgano boron compounds andfluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention include, but are not limitedto, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts in the present invention include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, are thought to form “weakly-coordinating” anionswhen combined with organometal or metallocene compounds, as disclosed inU.S. Pat. No. 5,919,983, the disclosure of which is incorporated hereinby reference in its entirety. Applicants also contemplate the use ofdiboron, or bis-boron, compounds or other bifunctional compoundscontaining two or more boron atoms in the chemical structure, such asdisclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the contentof which is incorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof metallocene compounds in the catalyst composition is in a range fromabout 0.1:1 to about 15:1. Typically, the amount of the fluoroorganoboron or fluoroorgano borate compound used is from about 0.5 moles toabout 10 moles of boron/borate compound per mole of metallocenecompounds (catalyst component I, catalyst component II, and any othermetallocene compound(s)). According to another aspect of this invention,the amount of fluoroorgano boron or fluoroorgano borate compound is fromabout 0.8 moles to about 5 moles of boron/borate compound per mole ofmetallocene compounds.

Ionizing Ionic Compounds

The present invention further provides a catalyst composition which cancomprise an ionizing ionic compound. An ionizing ionic compound is anionic compound that can function as a co-catalyst to enhance theactivity of the catalyst composition. While not intending to be bound bytheory, it is believed that the ionizing ionic compound is capable ofreacting with a metallocene compound and converting the metallocene intoone or more cationic metallocene compounds, or incipient cationicmetallocene compounds. Again, while not intending to be bound by theory,it is believed that the ionizing ionic compound can function as anionizing compound by completely or partially extracting an anionicligand, possibly a non-alkadienyl from the metallocene. However, theionizing ionic compound is an activator or co-catalyst regardless ofwhether it is ionizes the metallocene, abstracts a ligand in a fashionas to form an ion pair, weakens the metal-ligand bond in themetallocene, simply coordinates to a ligand, or activates themetallocene by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe metallocene compound(s) only. The activation function of theionizing ionic compound can be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositionthat does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethyl-phenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof. Ionizing ionic compounds usefulin this invention are not limited to these; other examples of ionizingionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938,the disclosures of which are incorporated herein by reference in theirentirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically include olefincompounds having from 2 to 30 carbon atoms per molecule and having atleast one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally contain a major amount of ethylene (>50 mole percent)and a minor amount of comonomer (<50 mole percent), though this is not arequirement. Comonomers that can be copolymerized with ethylene oftenhave from 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described above. Styrene can also be employedas a monomer in the present invention. In an aspect, the olefin monomeris a C₂-C₁₀ olefin; alternatively, the olefin monomer is ethylene; oralternatively, the olefin monomer is propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can comprise, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect ofthis invention, the olefin monomer in the polymerization processcomprises ethylene. In this aspect, examples of suitable olefincomonomers include, but are not limited to, propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene,styrene, and the like, or combinations thereof. According to one aspectof the present invention, the comonomer can comprise 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combinationthereof.

Generally, the amount of comonomer introduced into a reactor zone toproduce the copolymer is from about 0.01 to about 50 weight percent ofthe comonomer based on the total weight of the monomer and comonomer.According to another aspect of the present invention, the amount ofcomonomer introduced into a reactor zone is from about 0.01 to about 40weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a reactor zone is from about 0.1 to about 35 weight percentcomonomer based on the total weight of the monomer and comonomer. Yet,in another aspect, the amount of comonomer introduced into a reactorzone is from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. According to one aspect of the present invention, at least onemonomer/reactant is ethylene, so the polymerizations are either ahomopolymerization involving only ethylene, or copolymerizations with adifferent acyclic, cyclic, terminal, internal, linear, branched,substituted, or unsubstituted olefin. In addition, the catalystcompositions of this invention can be used in the polymerization ofdiolefin compounds including, but not limited to, 1,3-butadiene,isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Composition

The present invention employs catalyst compositions containing catalystcomponent I, catalyst component II, and at least one activator. Thesecatalyst compositions can be utilized to producepolyolefins—homopolymers, copolymers, and the like—for a variety ofend-use applications. Catalyst components I and II were discussed above.In aspects of the present invention, it is contemplated that catalystcomponent I can contain more than one metallocene compound and/orcatalyst component II can contain more than one metallocene compound.Further, additional metallocene compounds—other than those specified incatalyst component I or catalyst component II—can be employed in thecatalyst composition and/or the polymerization process, provided thatthe additional metallocene compound(s) does not detract from theadvantages disclosed herein. Additionally, more than one activator alsomay be utilized.

Generally, catalyst compositions of the present invention comprisecatalyst component I, catalyst component II, and at least one activator.In aspects of the invention, the at least one activator can comprise atleast one activator-support. Activator-supports useful in the presentinvention were disclosed above. Such catalyst compositions can furthercomprise one or more than one organoaluminum compound or compounds(suitable organoaluminum compounds also were discussed above). Thus, acatalyst composition of this invention can comprise catalyst componentI, catalyst component II, at least one activator-support, and at leastone organoaluminum compound. For instance, the at least oneactivator-support can comprise fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.Additionally, the at least one organoaluminum compound can comprisetrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof.

In another aspect of the present invention, a catalyst composition isprovided which comprises catalyst component I, catalyst component II, atleast one activator-support, and at least one organoaluminum compound,wherein this catalyst composition is substantially free of aluminoxanes,organoboron or organoborate compounds, ionizing ionic compounds, and/orother similar materials; alternatively, substantially free ofaluminoxanes; alternatively, substantially free or organoboron ororganoborate compounds; or alternatively, substantially free of ionizingionic compounds. In these aspects, the catalyst composition has catalystactivity, to be discussed below, in the absence of these additionalmaterials. For example, a catalyst composition of the present inventioncan consist essentially of catalyst component I, catalyst component II,an activator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising catalyst component I, catalyst component II, andan activator-support, can further comprise an optional co-catalyst.Suitable co-catalysts in this aspect include, but are not limited to,aluminoxane compounds, organoboron or organoborate compounds, ionizingionic compounds, and the like, or any combination thereof. More than oneco-catalyst can be present in the catalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprisecatalyst component I, catalyst component II, and at least one activator,wherein the at least one activator comprises at least one aluminoxanecompound, at least one organoboron or organoborate compound, at leastone ionizing ionic compound, or combinations thereof.

In a particular aspect contemplated herein, the catalyst composition isa dual catalyst composition comprising an activator (one or more thanone), only one catalyst component I metallocene compound, and only onecatalyst component II metallocene compound. In these and other aspects,the catalyst composition can comprise at least one activator; only onecompound having formula (A), formula (B), or a dinuclear compound formedfrom an alkenyl-substituted compound having formula (A), formula (B), ora combination thereof; and only one compound having formula (C), formula(D), formula (E), formula (F), or a dinuclear compound formed from analkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof. In some aspects, thecatalyst composition can comprise at least one activator, only onemetallocene compound having formula (A) or formula (B), and only onemetallocene compound having formula (C), formula (D), formula (E), orformula (F). For example, the catalyst composition can comprise at leastone activator, only one metallocene compound having formula (A), andonly one metallocene compound having formula (C); alternatively, thecatalyst composition can comprise at least one activator, only onemetallocene compound having formula (A), and only one metallocenecompound having formula (D); alternatively, the catalyst composition cancomprise at least one activator, only one metallocene compound havingformula (A), and only one metallocene compound having formula (E);alternatively, the catalyst composition can comprise at least oneactivator, only one metallocene compound having formula (A), and onlyone metallocene compound having formula (F); alternatively, the catalystcomposition can comprise at least one activator, only one metallocenecompound having formula (B), and only one metallocene compound havingformula (C); alternatively, the catalyst composition can comprise atleast one activator, only one metallocene compound having formula (B),and only one metallocene compound having formula (D); alternatively, thecatalyst composition can comprise at least one activator, only onemetallocene compound having formula (B), and only one metallocenecompound having formula (E); or alternatively, the catalyst compositioncan comprise at least one activator, only one metallocene compoundhaving formula (B), and only one metallocene compound having formula(F). In these aspects, only two metallocene compounds are present in thecatalyst composition, i.e., one catalyst component I ansa-metallocenecompound and one catalyst component II metallocene compound. It is alsocontemplated that a dual metallocene catalyst composition can containminor amounts of an additional metallocene compound(s), but this is nota requirement, and generally the dual catalyst composition can consistessentially of the aforementioned two metallocene compounds, and in thesubstantial absence of any additional metallocene compounds, wherein anyadditional metallocene compounds would not increase/decrease theactivity of the catalyst composition by more than about 10% from thecatalyst activity of the catalyst composition in the absence of theadditional metallocene compounds.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

The metallocene compound from catalyst component I, the metallocenecompound from catalyst component II, or both, can be precontacted withan olefinic monomer if desired, not necessarily the olefin monomer to bepolymerized, and an organoaluminum compound for a first period of timeprior to contacting this precontacted mixture with an activator-support.The first period of time for contact, the precontact time, between themetallocene compound, the olefinic monomer, and the organoaluminumcompound typically ranges from a time period of about 1 minute to about24 hours, for example, from about 0.05 hours to about 1 hour. Precontacttimes from about 10 minutes to about 30 minutes are also employed.Alternatively, the precontacting process is carried out in multiplesteps, rather than a single step, in which multiple mixtures areprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components are contacted forming a firstmixture, followed by contacting the first mixture with at least oneother catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component is fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component is fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or is fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, catalyst component I, catalyst component II,activator-support, organoaluminum co-catalyst, and optionally anunsaturated hydrocarbon) are contacted in the polymerization reactorsimultaneously while the polymerization reaction is proceeding.Alternatively, any two or more of these catalyst components can beprecontacted in a vessel prior to entering the reaction zone. Thisprecontacting step can be continuous, in which the precontacted productis fed continuously to the reactor, or it can be a stepwise or batchwiseprocess in which a batch of precontacted product is added to make acatalyst composition. This precontacting step can be carried out over atime period that can range from a few seconds to as much as severaldays, or longer. In this aspect, the continuous precontacting stepgenerally lasts from about 1 second to about 1 hour. In another aspect,the continuous precontacting step lasts from about 10 seconds to about45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of a catalyst component I metallocenecompound and/or catalyst component II metallocene, olefin monomer, andorganoaluminum co-catalyst is contacted with the activator-support, thiscomposition (with the addition of the activator-support) is termed the“postcontacted mixture.” The postcontacted mixture optionally remains incontact for a second period of time, the postcontact time, prior toinitiating the polymerization process. Postcontact times between theprecontacted mixture and the activator-support generally range fromabout 1 minute to about 24 hours. In a further aspect, the postcontacttime is in a range from about 0.05 hours to about 1 hour. Theprecontacting step, the postcontacting step, or both, can increase theproductivity of the polymer as compared to the same catalyst compositionthat is prepared without precontacting or postcontacting. However,neither a precontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture is immobilized, adsorbed, ordeposited thereon. Where heating is employed, the postcontacted mixturegenerally is heated to a temperature of from between about 0° F. toabout 150° F., or from about 40° F. to about 95° F.

According to one aspect of this invention, the weight ratio of catalystcomponent I to catalyst component II in the catalyst compositiongenerally is in a range from about 100:1 to about 1:100. In anotheraspect, the weight ratio is in a range from about 75:1 to about 1:75,from about 50:1 to about 1:50, or from about 30:1 to about 1:30. Yet, inanother aspect, the weight ratio of catalyst component I to catalystcomponent II in the catalyst composition is in a range from about 25:1to about 1:25. For instance, the weight ratio can be in a range fromabout 20:1 to about 1:20, from about 15:1 to about 1:15, from about 10:1to about 1:10, from about 5:1 to about 1:5; from about 4:1 to about 1:4,or from about 3:1 to about 1:3.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of metallocene(s) in the precontactedmixture is typically in a range from about 1:10 to about 100,000:1.Total moles of each component are used in this ratio to account foraspects of this invention where more than one olefin monomer and/or morethan one metallocene is employed in a precontacting step. Further, thismolar ratio can be in a range from about 10:1 to about 1,000:1 inanother aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support is in a range from about 10:1 to about 1:1000. If morethan one organoaluminum compound and/or more than one activator-supportis employed, this ratio is based on the total weight of each respectivecomponent. In another aspect, the weight ratio of the organoaluminumcompound to the activator-support is in a range from about 3:1 to about1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompounds (total of catalyst component I and catalyst component II) toactivator-support is in a range from about 1:1 to about 1:1,000,000. Ifmore than one activator-support is employed, this ratio is based on thetotal weight of the activator-support. In another aspect, this weightratio is in a range from about 1:5 to about 1:100,000, or from about1:10 to about 1:10,000. Yet, in another aspect, the weight ratio of themetallocene compounds to the activator-support is in a range from about1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated gP/(gAS·hr)). In another aspect, the catalystactivity is greater than about 150, greater than about 250, or greaterthan about 500 gP/(gAS·hr). In still another aspect, catalystcompositions of this invention are characterized by having a catalystactivity greater than about 1000, greater than about 1500, or greaterthan about 2000 gP/(gAS·hr). Yet, in another aspect, the catalystactivity is greater than about 2500 gP/(gAS·hr). This activity ismeasured under slurry polymerization conditions using isobutane as thediluent, at a polymerization temperature of about 90° C. and a reactorpressure of about 450 psig.

As discussed above, any combination of the metallocene compound fromcatalyst component I and/or from catalyst component II, theactivator-support, the organoaluminum compound, and the olefin monomer,can be precontacted in some aspects of this invention. When anyprecontacting occurs with an olefinic monomer, it is not necessary thatthe olefin monomer used in the precontacting step be the same as theolefin to be polymerized. Further, when a precontacting step among anycombination of the catalyst components is employed for a first period oftime, this precontacted mixture can be used in a subsequentpostcontacting step between any other combination of catalyst componentsfor a second period of time. For example, one or more metallocenecompounds, the organoaluminum compound, and 1-hexene can be used in aprecontacting step for a first period of time, and this precontactedmixture then can be contacted with the activator-support to form apostcontacted mixture that is contacted for a second period of timeprior to initiating the polymerization reaction. For example, the firstperiod of time for contact, the precontact time, between any combinationof the metallocene compound(s), the olefinic monomer, theactivator-support, and the organoaluminum compound can be from about 1minute to about 24 hours, from about 3 minutes to about 1 hour, or fromabout 10 minutes to about 30 minutes. The postcontacted mixtureoptionally is allowed to remain in contact for a second period of time,the postcontact time, prior to initiating the polymerization process.According to one aspect of this invention, postcontact times between theprecontacted mixture and any remaining catalyst components is from about1 minute to about 24 hours, or from about 0.1 hour to about 1 hour.

Polymerization Process

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention comprises contacting the catalystcomposition with an olefin monomer and optionally an olefin comonomerunder polymerization conditions to produce an olefin polymer, whereinthe catalyst composition comprises catalyst component I, catalystcomponent II, and at least one activator. Catalyst component I cancomprise a compound having formula (A); a compound having formula (B); adinuclear compound formed from an alkenyl-substituted compound havingformula (A), formula (B), or a combination thereof; or any combinationthereof. Catalyst component II can comprise a compound having formula(C); a compound having formula (D); a compound having formula (E); acompound having formula (F); a dinuclear compound formed from analkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof; or any combination thereof.

In accordance with one aspect of the invention, the polymerizationprocess employs a catalyst composition comprising catalyst component I,catalyst component II, and at least one activator, wherein the at leastone activator comprises at least one activator-support. This catalystcomposition can further comprise at least one organoaluminum compound.Suitable organoaluminum compounds can include, but are not limited to,trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or any combinationthereof.

In accordance with another aspect of the invention, the polymerizationprocess employs a catalyst composition comprising only one catalystcomponent I metallocene compound (e.g., a metallocene compound havingformula (A) or formula (B)); only one catalyst component II metallocenecompound (e.g., a metallocene compound having formula (C) or formula (D)or formula (E) or formula (F)); at least one activator-support; and atleast one organoaluminum compound.

In accordance with yet another aspect of the invention, thepolymerization process employs a catalyst composition comprisingcatalyst component I, catalyst component II, and at least one activator,wherein the at least one activator comprises at least one aluminoxanecompound, at least one organoboron or organoborate compound, at leastone ionizing ionic compound, or combinations thereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactors. As used herein, “polymerization reactor” includes anypolymerization reactor capable of polymerizing olefin monomers andcomonomers (one or more than one comonomer) to produce homopolymers,copolymers, terpolymers, and the like. The various types of reactorsinclude those that may be referred to as a batch reactor, slurryreactor, gas-phase reactor, solution reactor, high pressure reactor,tubular reactor, autoclave reactor, and the like, or combinationsthereof. The polymerization conditions for the various reactor types arewell known to those of skill in the art. Gas phase reactors may comprisefluidized bed reactors or staged horizontal reactors. Slurry reactorsmay comprise vertical or horizontal loops. High pressure reactors maycomprise autoclave or tubular reactors. Reactor types can include batchor continuous processes. Continuous processes could use intermittent orcontinuous product discharge. Processes may also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention may comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors may includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorsmay be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors may include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems may include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors maybe operated in series, in parallel, or both.

According to one aspect of the invention, the polymerization reactorsystem may comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer may becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes may comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent may beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies may be used forthis separation step including but not limited to, flashing that mayinclude any combination of heat addition and pressure reduction;separation by cyclonic action in either a cyclone or hydrocyclone; orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor may comprise at least one gas phase reactor. Such systems mayemploy a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream may bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product may be withdrawn from the reactor andnew or fresh monomer may be added to replace the polymerized monomer.Such gas phase reactors may comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor may comprise a tubular reactor or an autoclavereactor. Tubular reactors may have several zones where fresh monomer,initiators, or catalysts are added. Monomer may be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components may be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamsmay be intermixed for polymerization. Heat and pressure may be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor may comprise a solution polymerization reactor wherein themonomer/comonomer are contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer may be employed. If desired, themonomer/comonomer may be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation may be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactors suitable for the present invention may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature maybe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 110° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally is within a range fromabout 70° C. to about 90° C., or from about 75° C. to about 85° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig. Pressure for gas phasepolymerization is usually at about 200 to 500 psig. High pressurepolymerization in tubular or autoclave reactors is generally run atabout 20,000 to 75,000 psig. Polymerization reactors can also beoperated in a supercritical region occurring at generally highertemperatures and pressures. Operation above the critical point of apressure/temperature diagram (supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and optionally at least one olefin comonomer underpolymerization conditions to produce an olefin polymer. The olefinpolymer produced by the process can have a Mn in a range from about9,000 to about 30,000 g/mol. In addition, or alternatively, the olefinpolymer can have a ratio of Mw/Mn from about 4 to about 20. In addition,or alternatively, the olefin polymer can have a broad and/or a bimodalmolecular weight distribution. In addition, or alternatively, the olefinpolymer can have a short chain branch content that decreases asmolecular weight increases.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. Accordingly, anolefin polymerization process of this invention can comprise contactinga catalyst composition with an olefin monomer and optionally at leastone olefin comonomer under polymerization conditions to produce anolefin polymer, wherein the catalyst composition comprises catalystcomponent I, catalyst component II, and at least one activator, andwherein the polymerization process is conducted in the absence of addedhydrogen. As disclosed above, catalyst component I can comprise acompound having formula (A); a compound having formula (B); a dinuclearcompound formed from an alkenyl-substituted compound having formula (A),formula (B), or a combination thereof; or any combination thereof.Additionally, catalyst component II can comprise a compound havingformula (C); a compound having formula (D); a compound having formula(E); a compound having formula (F); a dinuclear compound formed from analkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof; or any combination thereof.

As one of ordinary skill in the art would recognize, hydrogen can begenerated in-situ by metallocene catalyst compositions in various olefinpolymerization processes, and the amount generated may vary dependingupon the specific catalyst composition and metallocene compound(s)employed, the type of polymerization process used, the polymerizationreaction conditions utilized, and so forth. Therefore, although hydrogenmay not be added to the polymerization reactor, it is contemplated thatpolymerization processes in accordance with this invention can beconducted in the presence of about 1 to about 1000 ppm hydrogen or, moretypically, in the presence of about 5 ppm to about 750 ppm, or in thepresence of about 10 ppm to about 500 ppm hydrogen. Hence, hydrogencontents in the polymerization reactor may be in a range from about 12ppm to about 475 ppm, from about 15 ppm to about 450 ppm, from about 20ppm to about 425 ppm, or from about 25 ppm to about 400 ppm.

While in many aspects of this invention, hydrogen is not added duringthe polymerization process, Applicants contemplate that the beneficialpolymer properties resulting from the use of the disclosed dual catalystcompositions (i.e., catalyst component I and catalyst component II) arenot limited only to circumstances where hydrogen is not added to thepolymerization reactor. For instance, Applicants contemplate that lowlevels of added hydrogen may be used, and the amount of added hydrogenmay depend on the desired polymer molecular weight and/or polymer meltindex, among other considerations.

According to one aspect of this invention, the ratio of hydrogen to theolefin monomer in the polymerization process can be controlled. Thisweight ratio generally can range from about 1 ppm to about 1000 ppm ofhydrogen, based on the weight of the olefin monomer. For instance, thereactant or feed ratio of hydrogen to olefin monomer can be controlledat a weight ratio which falls within a range from about 5 ppm to about900 ppm, from about 7 ppm to about 750 ppm, or from about 10 ppm toabout 500 ppm. Furthermore, the reactant or feed ratio of hydrogen toolefin monomer can be controlled at a weight ratio in a range from about15 ppm to about 475 ppm, from about 20 ppm to about 450 ppm, or fromabout 25 ppm to about 400 ppm, in some aspects of this invention.

In ethylene polymerizations, the feed ratio of hydrogen to ethylenemonomer, irrespective of comonomer(s) employed, may be controlled at aweight ratio within a range from about 1 ppm to about 1000 ppm;alternatively, from about 5 ppm to about 900 ppm; alternatively, fromabout 7 ppm to about 750 ppm; alternatively, from about 10 ppm to about500 ppm; alternatively, from about 15 ppm to about 475 ppm;alternatively, from about 20 ppm to about 450 ppm; or alternatively,from about 25 ppm to about 400 ppm.

In another aspect, the feed or reactant ratio of hydrogen to olefinmonomer is maintained substantially constant during the polymerizationrun for a particular polymer grade. That is, the hydrogen:olefin ratiois selected at a particular ratio within the range from about 1 ppm toabout 1000 ppm, and maintained at the ratio to within about +/−25%during the polymerization run. For instance, if the target ratio is 100ppm, then maintaining the hydrogen:olefin ratio substantially constantwould entail maintaining the feed ratio between about 75 ppm and about125 ppm. Further, the addition of comonomer (or comonomers) can be, andgenerally is, substantially constant throughout the polymerization runfor a particular polymer grade.

However, in another aspect, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

If the resultant polymer produced in accordance with the presentinvention is, for example, a polymer or copolymer of ethylene, itsproperties can be characterized by various analytical techniques knownand used in the polyolefin industry. Articles of manufacture can beformed from, and/or can comprise, the ethylene polymers of thisinvention, whose typical properties are provided below.

Polymers of ethylene (copolymers, terpolymers, etc.) produced inaccordance with this invention generally have a melt index from about0.001 to about 100 g/10 min. Melt indices in the range from about 0.001to about 75 g/10 min, from about 0.01 to about 50 g/10 min, or fromabout 0.05 to about 30 g/10 min, are contemplated in some aspects ofthis invention. For example, a polymer of the present invention can havea melt index (MI) in a range from about 0.05 to about 25, or from about0.1 to about 10 g/10 min.

Ethylene polymers produced in accordance with this invention can have aratio of HLMI/MI in a range from about 5 to about 150, such as, forexample, from about 10 to about 125, from about 10 to about 100, fromabout 15 to about 90, from about 15 to about 80, from about 20 to about70, or from about 25 to about 65.

The density of ethylene-based polymers produced using the catalystsystems and processes disclosed herein typically falls within the rangefrom about 0.88 to about 0.97 g/cm³. In one aspect of this invention,the density of an ethylene polymer is in a range from about 0.90 toabout 0.95 g/cm³. Yet, in another aspect, the density is in a range fromabout 0.91 to about 0.945 g/cm³, such as, for example, from about 0.92to about 0.945 g/cm³.

Ethylene polymers, such as copolymers and terpolymers, within the scopeof the present invention generally have a polydispersity index—a ratioof the weight-average molecular weight (Mw) to the number-averagemolecular weight (Mn)—in a range from about 4 to about 20. In someaspects disclosed herein, the ratio of Mw/Mn is in a range from about 4to about 18, from about 4 to about 16, from about 4.2 to about 16, orfrom about 4.2 to about 15. For instance, the Mw/Mn of the polymer canbe within a range from about 4.2 to about 12, from about 4.2 to about10, from about 4.3 to about 8, or from about 4.3 to about 7.5.

The ratio of Mz/Mw for the polymers of this invention often is in arange from about 2.2 to about 10. Mz is the z-average molecular weight,and Mw is the weight-average molecular weight. In accordance with oneaspect, the Mz/Mw of the ethylene polymers of this invention is in arange from about 2.2 to about 8, from about 2.2 to about 7, from about2.3 to about 7, from about 2.4 to about 6, or from about 2.5 to about 5.

Ethylene polymers can have, in some aspects of this invention, a Mnwithin a range from about 7,000 to about 40,000 g/mol, such as, forexample, from about 8,000 to about 35,000, or from about 9,000 to about30,000 g/mol. Accordingly, the Mn of the ethylene polymer can be withina range from about 9,000 to about 28,000 g/mol in aspects of thisinvention; alternatively, from about 9,500 to about 26,000 g/mol;alternatively, from about 9,500 to about 25,000 g/mol; alternatively,from about 10,000 to about 25,000 g/mol; alternatively, from about10,500 to about 24,000 g/mol; or alternatively, from about 11,000 toabout 23,000 g/mol.

Ethylene polymers (e.g., copolymers) produced using the polymerizationprocesses and catalyst systems described above can have a short chainbranch content that decreases as molecular weight increases, i.e., thehigher molecular weight components of the polymer generally have lowercomonomer incorporation than the lower molecular weight components, orthere is decreasing comonomer incorporation with increasing molecularweight. Often, the amount of comonomer incorporation at higher molecularweights can be about 20% lower, or about 30% lower, or about 50% lower,or about 70% lower, or about 90% lower, than at lower molecular weights.For instance, the number of short chain branches (SCB) per 1000 totalcarbon atoms can be greater at Mn than at Mw. Ethylene polymers of thisinvention may have a SCBD (short chain branching distribution) that issimilar to the SCBD found in ethylene polymers produced usingtraditional Ziegler-Natta catalyst systems.

In addition, the SCBD (short chain branching distribution) of polymersof the present invention can be characterized by the ratio of the numberof SCB per 1000 total carbon atoms of the polymer at D90 to the numberof SCB per 1000 total carbon atoms of the polymer at D10, i.e., (SCB atD90)/(SCB at D10). D90 is the molecular weight at which 90% of thepolymer by weight has higher molecular weight, and D10 is the molecularweight at which 10% of the polymer by weight has higher molecularweight. D90 and D10 are depicted graphically in FIG. 1 for a molecularweight distribution curve as a function of increasing logarithm of themolecular weight. In accordance with one aspect of the presentinvention, a ratio of the number of short chain branches (SCB) per 1000total carbon atoms of the polymer at D90 to the number of SCB per 1000total carbon atoms of the polymer at D10 is in a range from about 1.1 toabout 20. For instance, the ratio of the number of short chain branches(SCB) per 1000 total carbon atoms of the polymer at D90 to the number ofSCB per 1000 total carbon atoms of the polymer at D10 can be in a rangefrom about 1.1 to about 10, or from about 1.2 to about 6, or from about1.2 to about 3. Generally, polymers disclosed herein have from about 1to about 20 short chain branches (SCB) per 1000 total carbon atoms atD90, and this typically varies with the density of the polymer.

Likewise, the SCBD of polymers of the present invention can becharacterized by the ratio of the number of SCB per 1000 total carbonatoms of the polymer at D85 to the number of SCB per 1000 total carbonatoms of the polymer at D15, i.e., (SCB at D85)/(SCE at D15). D85 is themolecular weight at which 85% of the polymer by weight has highermolecular weight, and D15 is the molecular weight at which 15% of thepolymer by weight has higher molecular weight. In accordance with oneaspect of the present invention, a ratio of the number of short chainbranches (SCB) per 1000 total carbon atoms of the polymer at D85 to thenumber of SCB per 1000 total carbon atoms of the polymer at D15 is in arange from about 1.1 to about 18. For instance, the ratio of the numberof short chain branches (SCB) per 1000 total carbon atoms of the polymerat D85 to the number of SCB per 1000 total carbon atoms of the polymerat D15 can be in a range from about 1.1 to about 10, or from about 1.2to about 6, or from about 1.2 to about 4, or from about 1.2 to about2.5.

An illustrative and non-limiting example of an ethylene polymer of thepresent invention can be characterized by a broad and/or bimodalmolecular weight distribution; and/or a Mn in a range from about 9,000to about 30,000 g/mol; and/or a ratio of Mw/Mn from about 4 to about 20;and/or a ratio of the number of SCB per 1000 total carbon atoms of thepolymer at D90 to the number of SCB per 1000 total carbon atoms of thepolymer at D10 in a range from 1.1 to about 10; and/or a ratio of thenumber of SCB per 1000 total carbon atoms of the polymer at D85 to thenumber of SCB per 1000 total carbon atoms of the polymer at D15 in arange from 1.1 to about 8. Such illustrative polymers also may befurther characterized by a MI in a range from about 0.01 to about 50g/10 min, and/or a ratio of HLMI/MI in a range from about 20 to about80, and/or a density in a range from about 0.91 to about 0.945 g/cm³.

Polymers of ethylene, whether homopolymers, copolymers, terpolymers, andso forth, can be formed into various articles of manufacture. Articleswhich can comprise polymers of this invention include, but are notlimited to, an agricultural film, an automobile part, a bottle, a drum,a fiber or fabric, a food packaging film or container, a food servicearticle, a fuel tank, a geomembrane, a household container, a liner, amolded product, a medical device or material, a pipe, a sheet or tape, atoy, and the like. Various processes can be employed to form thesearticles. Non-limiting examples of these processes include injectionmolding, blow molding, rotational molding, film extrusion, sheetextrusion, profile extrusion, thermoforming, and the like. Additionally,additives and modifiers are often added to these polymers in order toprovide beneficial polymer processing or end-use product attributes.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight.

High load melt index (HLMI, g/10 min) was determined in accordance withASTM D1238 at 190° C. with a 21,600 gram weight.

Polymer density was determined in grams per cubic centimeter (g/cm³) ona compression molded sample, cooled at about 15° C. per hour, andconditioned for about 40 hours at room temperature in accordance withASTM D1505 and ASTM D1928, procedure C.

Molecular weights and molecular weight distributions were obtained usinga PL 220 SEC high temperature chromatography unit (Polymer Laboratories)with trichlorobenzene (TCB) as the solvent, with a flow rate of 1mL/minute at a temperature of 145° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L wasused as a stabilizer in the TCB. An injection volume of 200 μL was usedwith a nominal polymer concentration of 1.5 mg/mL. Dissolution of thesample in stabilized TCB was carried out by heating at 150° C. for 5hours with occasional, gentle agitation. The columns used were threePLgel Mixed A LS columns (7.8×300 mm) and were calibrated with a broadlinear polyethylene standard (Phillips Marlex® BHB 5003) for which themolecular weight had been determined.

Short chain branching distribution (SCBD) data was obtained using aSEC-FTIR high temperature heated flow cell (Polymer Laboratories) asdescribed by P. J. DesLauriers, D. C. Rohlfing, and E. T. Hsieh,Polymer, 43, 159 (2002).

The sulfated alumina activator-support (abbreviated SA) employed inExamples 1-6 and 11-16 was prepared in accordance with the followingprocedure. Bohemite was obtained from W.R. Grace Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g anda pore volume of about 1.3 mL/g. This material was obtained as a powderhaving an average particle size of about 100 microns. This material wasimpregnated to incipient wetness with an aqueous solution of ammoniumsulfate to equal about 15% sulfate. This mixture was then placed in aflat pan and allowed to dry under vacuum at approximately 110° C. forabout 16 hours.

To calcine the support, about 10 grams of this powdered mixture wereplaced in a 1.75-inch quartz tube fitted with a sintered quartz disk atthe bottom. While the powder was supported on the disk, air (nitrogencan be substituted) dried by passing through a 13× molecular sievecolumn, was blown upward through the disk at the linear rate of about1.6 to 1.8 standard cubic feet per hour. An electric furnace around thequartz tube was then turned on and the temperature was raised at therate of about 400° C. per hour to the desired calcining temperature ofabout 600° C. At this temperature, the powder was allowed to fluidizefor about three hours in the dry air. Afterward, the sulfated aluminaactivator-support (SA) was collected and stored under dry nitrogen, andwas used without exposure to the atmosphere.

The fluorided silica-alumina activator-support (abbreviated FSA)employed in Examples 7-10 was prepared in accordance with the followingprocedure. A silica-alumina was obtained from W.R. Grace Companycontaining about 13% alumina by weight and having a surface area ofabout 400 m²/g and a pore volume of about 1.2 mL/g. This material wasobtained as a powder having an average particle size of about 70microns. Approximately 100 grams of this material were impregnated witha solution containing about 200 mL of water and about 10 grams ofammonium hydrogen fluoride, resulting in a damp powder having theconsistency of wet sand. This mixture was then placed in a flat pan andallowed to dry under vacuum at approximately 110° C. for about 16 hours.

To calcine the support, about 10 grams of this powdered mixture wereplaced in a 1.75-inch quartz tube fitted with a sintered quartz disk atthe bottom. While the powder was supported on the disk, air (nitrogencan be substituted) dried by passing through a 13× molecular sievecolumn, was blown upward through the disk at the linear rate of about1.6 to 1.8 standard cubic feet per hour. An electric furnace around thequartz tube was then turned on and the temperature was raised at therate of about 400° C. per hour to the desired calcining temperature ofabout 450° C. At this temperature, the powder was allowed to fluidizefor about three hours in the dry air. Afterward, the fluoridedsilica-alumina activator-support (FSA) was collected and stored underdry nitrogen, and was used without exposure to the atmosphere.

The polymerization runs were conducted in a one-gallon (3.8-liter)stainless steel reactor as follows. First, the reactor was purged withnitrogen and then with isobutane vapor. Approximately 0.3-1.0 mmol ofeither triisobutylaluminum (TIBA) or triethylaluminum (TEA), 100-200 mgof activator-support SA or FSA, and the desired amount of catalystcomponent I and/or catalyst component II (see below for structures ofthese components) were added in that order through a charge port whileventing isobutane vapor. The charge port was closed and about 2 L ofisobutane were added. The contents of the reactor were stirred andheated to 85-90° C. Then, 8-25 grams of 1-hexene were added into thereactor (no 1-hexene added for Examples 13-16), followed by theintroduction of ethylene. Hydrogen was used in Examples 14-16, with thehydrogen added at a fixed mass ratio with respect to the ethylene flow.Hydrogen was stored in a 340-mL pressure vessel and added with theethylene via an automated feeding system, while the total reactorpressure was maintained at the desired pressure in the 390-550 psigrange by the combined ethylene/hydrogen (if used)/isobutane addition.The reactor was maintained and controlled at either 85° C. or 90° C.throughout the 30-minute run time of the polymerization. Uponcompletion, the isobutane and ethylene were vented from the reactor, thereactor was opened, and the polymer product was collected and dried.

Examples 1-12 Polymers Produced Using a Dual Catalyst System

Catalyst component I metallocene compounds used in these examples hadthe following structures:

Catalyst component II metallocene compounds used in these examples hadthe following structures:

These metallocene compounds can be prepared in accordance with anysuitable method. Representative techniques are described in U.S. Pat.Nos. 7,026,494, 7,199,073, 7,312,283, 7,456,243, and 7,521,572, and U.S.Patent Publication 2009/0088543, the disclosures of which areincorporated herein by reference in their entirety.

The polymerization conditions for Examples 1-12 are summarized in TableI, while the resultant polymer properties for Examples 1-12 aresummarized in Table II. The weight ratio of catalyst components I:II inExamples 1-12 was within a range from about 4:1 to about 1:2. The Mn ofthe polymers of Examples 1-12 was within a range from about 11,000 toabout 25,000 g/mol.

FIG. 2 illustrates the molecular weight distributions of the polymers ofExamples 1-4, FIG. 3 illustrates the molecular weight distributions ofthe polymers of Examples 5-6, and FIG. 4 illustrates the molecularweight distributions of the polymers of Examples 7-10. FIGS. 2-4demonstrate that the polymers of Examples 1-10 have a broad and/orbimodal MWD.

FIGS. 5-8 illustrate the MWD and the SCBD of the polymers of Examples 5,6, 11, and 12, respectively. These polymers have a bimodal MWD and, inaddition, the SCB content decreases as molecular weight increases.

TABLE I Polymerization Conditions for Examples 1-12. Catalyst CatalystTime Temperature Reactor Pressure 1-hexene Activator- Alkyl ExampleComponent I Component II (min) (° C.) (psi) (g) Support Aluminum 1 1.5mg I-1 1 mg II-1 30 90 390 8 150 mg SA 0.6 mmol TIBA 2 2 mg I-1 0.5 mgII-1 30 90 390 8 150 mg SA 0.6 mmol TIBA 3 2 mg I-1 0.8 mg II-1 30 90390 8 150 mg SA 0.6 mmol TIBA 4 2 mg I-1 1 mg II-1 30 90 390 8 150 mg SA0.6 mmol TIBA 5 2 mg I-1 1 mg II-1 30 90 390 15 150 mg SA 0.6 mmol TIBA6 1.5 mg I-1 1 mg II-1 30 90 390 15 150 mg SA 0.6 mmol TIBA 7 1.5 mg I-21.5 mg II-2 30 90 550 10 200 mg FSA 0.5 mmol TEA 8 0.5 mg I-2 0.5 mgII-3 30 90 550 25 200 mg FSA 1 mmol TIBA 9 1 mg I-2 0.75 mg II-4 30 90550 25 200 mg FSA 1 mmol TEA 10 0.5 mg I-3 1 mg II-5 30 85 450 20 150 mgFSA 1 mmol TEA 11 1.2 mg I-1 1 mg II-1 30 85 390 15 200 mg SA 0.8 mmolTIBA 12 1.2 mg I-1 1 mg II-1 30 85 390 25 200 mg SA 0.8 mmol TIBA

TABLE II Polymer Properties of Examples 1-12. g PE MI HLMI Density Mn MwMz Example Produced (g/10 min) (g/10 min) (g/cc) (g/mol) (g/mol) (g/mol)Mw/Mn Mz/Mw 1 168 1.7 68 0.9408 19,000 110,000 310,500 5.8 2.8 2 20536.9 838 — 12,300 55,900 233,800 4.5 4.2 3 198 7.8 498 0.9426 13,50075,800 252,600 5.6 3.3 4 161 2.4 123 0.9423 16,900 99,400 303,300 5.93.1 5 197 5.7 306 0.9388 12,700 75,500 234,600 5.9 3.1 6 197 3.8 1810.9368 14,300 84,200 244,600 5.9 2.9 7 112 0.2 6.0 0.9467 23,100 234,2001,067,000 10.1 4.6 8 468 0.2 5.7 0.9381 24,800 236,800 601,200 5.9 2.5 9116 <0.1 5.6 0.9324 11,000 139,500 981,200 12.6 7.0 10 106 0.1 6.00.9316 24,200 188,000 643,700 7.1 3.4 11 286 2.3 84.2 0.9355 17,600101,100 276,900 5.8 2.7 12 151 1.1 31.4 0.9225 18,700 114,900 261,2006.1 2.3

Examples 13-16 Polymers Produced Using a Catalyst System Containing aSingle Catalyst Component I Metallocene

The catalyst component I metallocene compound used in these examples hadthe following structure:

The polymerization conditions for Examples 13-16 are summarized in TableIII, while the resultant polymer properties for Examples 13-16 aresummarized in Table IV. FIG. 9 illustrates the molecular weightdistributions of the polymers of Examples 13-16. As shown in TablesIII-IV and FIG. 9, unexpectedly, the molecular weight distributions ofthe polymers of Examples 13-16 were largely unaffected by the amount ofhydrogen added to the reactor.

TABLE III Polymerization Conditions for Examples 13-16. CatalystCatalyst Time Temperature Reactor Pressure H₂/ethylene Activator- AlkylExample Component I Component II (min) (° C.) (psi) (ppm) SupportAluminum 13 2 mg I-1 None 30 90 390 0 100 mg SA 0.3 mmol TIBA 14 2 mgI-1 None 30 90 390 100 100 mg SA 0.3 mmol TIBA 15 2 mg I-1 None 30 90390 200 100 mg SA 0.3 mmol TIBA 16 2 mg I-1 None 30 90 390 300 100 mg SA0.3 mmol TIBA

TABLE IV Polymer Properties of Examples 13-16. g PE MI HLMI Mn Mw MzExample Produced (g/10 min) (g/10 min) (g/mol) (g/mol) (g/mol) Mw/MnMz/Mw 13 158 >200 Too high 12,800 28,400 49,500 2.2 1.7 14 167 >200 Toohigh 10,900 28,200 49,400 2.6 1.8 15 142 >200 Too high 12,900 30,20058,500 2.3 1.9 16 184 >200 Too high 10,300 28,500 51,000 2.8 1.8

1. An olefin polymerization process, the process comprising: contactinga catalyst composition with an olefin monomer and optionally at leastone olefin comonomer under polymerization conditions to produce anolefin polymer, wherein the catalyst composition comprises catalystcomponent I, catalyst component II, and at least one activator, wherein:the olefin polymer has a Mn in a range from about 7,000 to about 40,000g/mol; catalyst component I comprises: a compound having formula (A); acompound having formula (B); a dinuclear compound formed from analkenyl-substituted compound having formula (A), formula (B), or acombination thereof; or any combination thereof, wherein: formula (A) is

wherein: M¹ is Zr or Hf; X¹ and X² are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E¹ is C or Si; R¹ and R² are independently H, ahydrocarbyl group having up to 18 carbon atoms, or R¹ and R² areconnected to form a cyclic or heterocyclic group having up to 18 carbonatoms; and R³ is H or a hydrocarbyl or hydrocarbylsilyl group having upto 18 carbon atoms; and formula (B) is

wherein: M² is Zr or Hf; X³ is F; Cl; Br; I; methyl; benzyl; phenyl; H;BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl group having up to 18carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, ora hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E²is C or Si; R⁴ is H or a hydrocarbyl group having up to 18 carbon atoms;and R⁵ is a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbonatoms; and catalyst component II comprises: a compound having formula(C); a compound having formula (D); a compound having formula (E); acompound having formula (F); a dinuclear compound formed from analkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof; or any combination thereof,wherein: formula (C) is

wherein: M³ is Zr or Hf; X⁴ and X⁵ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E³ is a bridging group selected from: a cyclic orheterocyclic bridging group having up to 18 carbon atoms, a bridginggroup having the formula >E^(3A)R^(7A)R^(8A), wherein E^(3A) is C or Si,and R^(7A) and R^(8A) are independently H or a hydrocarbyl group havingup to 18 carbon atoms, a bridging group having the formula—CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B), R^(8B), R^(7C), andR^(8C) are independently H or a hydrocarbyl group having up to 10 carbonatoms, or a bridging group having the formula—SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—, wherein R^(7D), R^(8D), R^(7E), andR^(8E) are independently H or a hydrocarbyl group having up to 10 carbonatoms; R⁹ and R¹⁰ are independently H or a hydrocarbyl group having upto 18 carbon atoms; and Cp¹ is a cyclopentadienyl or indenyl group, anysubstituent on Cp¹ is H or a hydrocarbyl or hydrocarbylsilyl grouphaving up to 18 carbon atoms; formula (D) is

wherein: M⁴ is Zr or Hf; X⁶ and X⁷ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E⁴ is a bridging group selected from: a cyclic orheterocyclic bridging group having up to 18 carbon atoms, a bridginggroup having the formula >E^(4A)R^(12A)R^(13A), wherein E^(4A) is C orSi, and R^(12A) and R^(13A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms, a bridging group having the formula—CR^(12B)R^(13B)—CR^(12C)R^(13C)—, wherein R^(12B), R^(13B), R^(12C),and R^(13C) are independently H or a hydrocarbyl group having up to 10carbon atoms, or a bridging group having the formula—SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, wherein R^(12D), R^(13D), R^(12E),and R^(13E) are independently H or a hydrocarbyl group having up to 10carbon atoms; and R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are independently H or ahydrocarbyl group having up to 18 carbon atoms; formula (E) is

wherein: M⁵ is Zr or Hf; X⁸ and X⁹ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; and E⁵ is a bridging group selected from: acyclic or heterocyclic bridging group having up to 18 carbon atoms, abridging group having the formula >E^(5A)R^(20A)R^(21A), wherein E^(5A)is C or Si, and R^(20A) and R^(21A) are independently H or a hydrocarbylgroup having up to 18 carbon atoms, a bridging group having the formula—(CH₂)_(n)—, wherein n is an integer from 2 to 6, inclusive, or abridging group having the formula —SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—,wherein R^(20B), R^(21B), R^(20C), and R^(21C) are independently H or ahydrocarbyl group having up to 10 carbon atoms; and formula (F) is

wherein: M⁶ is Zr or Hf; X¹⁰ and X¹¹ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; and Cp² and Cp³ are independently acyclopentadienyl, indenyl or fluorenyl group, any substituent on Cp² andCp³ is independently H or a hydrocarbyl group having up to 18 carbonatoms.
 2. The process of claim 1, wherein the catalyst compositioncomprises at least one activator, only one ansa-metallocene compoundhaving formula (A) or formula (B), and only one metallocene compoundhaving formula (C), formula (D), formula (E), or formula (F).
 3. Theprocess of claim 1, wherein the at least one activator comprises atleast one activator-support comprising a solid oxide treated with anelectron-withdrawing anion, wherein: the solid oxide comprises silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, or any combination thereof.
 4. Theprocess of claim 1, wherein the catalyst composition further comprisesat least one organoaluminum compound having the formula:Al(X^(A))_(m)(X^(B))_(3−m), wherein: X^(A) is a hydrocarbyl; X^(B) is analkoxide or an aryloxide, a halide, or a hydride; and m is from 1 to 3,inclusive.
 5. The process of claim 4, wherein: the at least oneorganoaluminum compound comprises trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, or any combinationthereof; and the at least one activator comprises at least oneactivator-support, and wherein the at least one activator-supportcomprises fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or any combination thereof.
 6. The process ofclaim 1, wherein the at least one activator comprises at least onealuminoxane compound, at least one organoboron or organoborate compound,at least one ionizing ionic compound, or any combination thereof.
 7. Theprocess of claim 1, wherein catalyst component I comprises a compoundhaving formula (A), and wherein: X¹ and X² are independently F, Cl, Br,I, methyl, benzyl, or phenyl; and R¹, R², and R³ are independentlymethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, or benzyl.
 8. The process of claim 1,wherein catalyst component I comprises a compound having formula (B),and wherein: X³ is F, Cl, Br, I, methyl, benzyl, or phenyl; R⁴ ismethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, or benzyl; and R⁵ is methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, phenyl, tolyl, or benzyl.
 9. The process of claim 1, whereincatalyst component II comprises a compound having formula (C), andwherein: X⁴ and X⁵ are independently F, Cl, Br, I, benzyl, phenyl, ormethyl; E³ is a bridging group selected from: a cyclopentyl orcyclohexyl group, a bridging group having the formula>E^(3A)R^(7A)R^(8A), wherein E^(3A) is C or Si, and R^(7A) and R^(8A)are independently H, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, or benzyl,a bridging group having the formula —CR^(7B)R^(8B)—CR^(7C)R^(8C)—,wherein R^(7B), R^(8B), R^(7C), and R^(8C) are independently H ormethyl, or a bridging group having the formula—SiR^(7D)R^(8D)—SiR^(7E)R^(8E)—, wherein R^(7D), R^(8D), R^(7E), andR^(8E) are independently H or methyl; and R⁹ and R¹⁰ are independently Hor t-butyl.
 10. The process of claim 1, wherein catalyst component IIcomprises a compound having formula (D), and wherein: X⁶ and X⁷ areindependently F, Cl, Br, I, benzyl, phenyl, or methyl; E⁴ is a bridginggroup selected from: a cyclopentyl or cyclohexyl group, a bridging grouphaving the formula >E^(4A)R^(12A)R^(13A), wherein E^(4A) is C or Si, andR^(12A) and R^(13A) are independently H, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, abridging group having the formula —CR^(12B)R^(13B)—CR^(12C)R^(13C)—,wherein R^(12B), R^(13B), R_(12C, and R) ^(13C) are independently H ormethyl, or a bridging group having the formula—SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, wherein R^(12D), R^(13D), R^(12E),and R^(13E) are independently H or methyl; and R¹⁴, R¹⁵, R¹⁶, and R¹⁷are independently H or t-butyl.
 11. The process of claim 1, whereincatalyst component II comprises a compound having formula (E), andwherein: X⁸ and X⁹ are independently F, Cl, Br, I, benzyl, phenyl, ormethyl; and E⁵ is a bridging group selected from: a cyclopentyl orcyclohexyl group, bridging group having the formula>E^(5A)R^(20A)R^(21A), wherein E^(5A) is C or Si, and R^(20A) andR^(21A) are independently H, methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl,or benzyl, a bridging group having the formula —(CH₂)_(n)—, wherein n isequal to 2, 3, or 4, or a bridging group having the formula—SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—, wherein R^(20B), R^(21B), R^(20C),and R^(21C) are independently H or methyl.
 12. The process of claim 1,wherein catalyst component II comprises a compound having formula (F),and wherein: X¹⁰ and X¹¹ are independently F, Cl, Br, I, benzyl, phenyl,or methyl; and Cp² and Cp³ are independently a cyclopentadienyl orindenyl group, any substituent on Cp² and Cp³ is independently H,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, tolyl,or benzyl.
 13. The process of claim 1, wherein a weight ratio ofcatalyst component I to catalyst component II in the catalystcomposition is in a range from about 100:1 to about 1:100.
 14. Theprocess of claim 1, wherein the process is conducted in a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, or a combination thereof.15. The process of claim 1, wherein the olefin monomer is ethylene, andthe at least one olefin comonomer comprises propylene, 1-butene,2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene,3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene,styrene, or a mixture thereof.
 16. The process of claim 1, wherein theprocess is conducted in the absence of added hydrogen.
 17. The processof claim 1, wherein the process is conducted in the presence of about 10ppm to about 500 ppm hydrogen.
 18. The process of claim 1, wherein: thepolymer has a Mn in a range from about 9,000 to about 30,000 g/mol; orthe polymer has a ratio of the number of short chain branches (SCB) per1000 total carbon atoms of the polymer at D90 to the number of SCB per1000 total carbon atoms of the polymer at D10 in a range from 1.1 toabout 20; or both.
 19. An olefin polymerization process, the processcomprising: contacting a catalyst composition with an olefin monomer andat least one olefin comonomer under polymerization conditions to producean olefin polymer, wherein the catalyst composition comprises catalystcomponent I, catalyst component II, and at least one activator, wherein:the olefin polymer has a Mn in a range from about 9,000 to about 30,000g/mol; catalyst component I comprises: a compound having formula (A); acompound having formula (B); a dinuclear compound formed from analkenyl-substituted compound having formula (A), formula (B), or acombination thereof; or any combination thereof, wherein: formula (A) is

wherein: M¹ is Zr or Hf; X¹ and X² are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E¹ is C or Si; R¹ and R² are independently H, ahydrocarbyl group having up to 18 carbon atoms, or R¹ and R² areconnected to form a cyclic or heterocyclic group having up to 18 carbonatoms; and R³ is H or a hydrocarbyl or hydrocarbylsilyl group having upto 18 carbon atoms; and formula (B) is

wherein: M² is Zr or Hf; X³ is F; Cl; Br; I; methyl; benzyl; phenyl; H;BH₄; OBR₂ or SO₃R, wherein R is an alkyl or aryl group having up to 18carbon atoms; or a hydrocarbyloxide group, a hydrocarbylamino group, ora hydrocarbylsilyl group, any of which having up to 18 carbon atoms; E²is C or Si; R⁴ is H or a hydrocarbyl group having up to 18 carbon atoms;and R⁵ is a hydrocarbyl or hydrocarbylsilyl group having up to 18 carbonatoms; and catalyst component II comprises: a compound having formula(C); a compound having formula (D); a compound having formula (E); acompound having formula (F); a dinuclear compound formed from analkenyl-substituted compound having formula (C), formula (D), formula(E), formula (F), or a combination thereof; or any combination thereof,wherein: formula (C) is

wherein: M³ is Zr or Hf; X⁴ and X⁵ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E³ is a bridging group selected from: a cyclic orheterocyclic bridging group having up to 18 carbon atoms, a bridginggroup having the formula >E^(3A)R^(7A)R^(8A), wherein E^(3A) is C or Si,and R^(7A) and R^(8A) are independently H or a hydrocarbyl group havingup to 18 carbon atoms, a bridging group having the formula—CR^(7B)R^(8B)—CR^(7C)R^(8C)—, wherein R^(7B), R^(8B), R^(7C), andR^(8C) are independently H or a hydrocarbyl group having up to 10 carbonatoms, or a bridging group having the formula—SiR^(7D)R^(8D)SiR^(7E)R^(8E)—, wherein R^(7D), R^(8D), R^(7E), andR^(8E) are independently H or a hydrocarbyl group having up to 10 carbonatoms; R⁹ and R¹⁰ are independently H or a hydrocarbyl group having upto 18 carbon atoms; and Cp¹ is a cyclopentadienyl or indenyl group, anysubstituent on Cp¹ is H or a hydrocarbyl or hydrocarbylsilyl grouphaving up to 18 carbon atoms; formula (D) is

wherein: M⁴ is Zr or Hf; X⁶ and X⁷ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; E⁴ is a bridging group selected from: a cyclic orheterocyclic bridging group having up to 18 carbon atoms, a bridginggroup having the formula >E^(4A)R^(12A)R^(13A), wherein E^(4A) is C orSi, and R^(12A) and R^(13A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms, a bridging group having the formula—CR^(12B)R^(13B)—CR^(12C)R^(13C)—, wherein R^(12B), R^(13B), R^(12C),and R^(13C) are independently H or a hydrocarbyl group having up to 10carbon atoms, or a bridging group having the formula—SiR^(12D)R^(13D)—SiR^(12E)R^(13E)—, wherein R^(12D), R^(13D), R^(12E),and R^(13E) are independently H or a hydrocarbyl group having up to 10carbon atoms; and R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are independently H or ahydrocarbyl group having up to 18 carbon atoms; formula (E) is

wherein: M⁵ is Zr or Hf; X⁸ and X⁹ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; and E⁵ is a bridging group selected from: acyclic or heterocyclic bridging group having up to 18 carbon atoms, abridging group having the formula >E^(5A)R^(20A)R^(21A), wherein E^(5A)is C or Si, and R^(20A) and R^(21A) are independently H or a hydrocarbylgroup having up to 18 carbon atoms, a bridging group having the formula—(CH₂)_(n)—, wherein n is an integer from 2 to 6, inclusive, or abridging group having the formula —SiR^(20B)R^(21B)—SiR^(20C)R^(21C)—,wherein R^(20B), R^(21B), R^(20C), and R^(21C) are independently H or ahydrocarbyl group having up to 10 carbon atoms; and formula (F) is

wherein: M⁶ is Zr or Hf; X¹⁰ and X¹¹ are independently F; Cl; Br; I;methyl; benzyl; phenyl; H; BH₄; OBR₂ or SO₃R, wherein R is an alkyl oraryl group having up to 18 carbon atoms; or a hydrocarbyloxide group, ahydrocarbylamino group, or a hydrocarbylsilyl group, any of which havingup to 18 carbon atoms; and Cp² and Cp³ are independently acyclopentadienyl, indenyl or fluorenyl group, any substituent on Cp² andCp³ is independently H or a hydrocarbyl group having up to 18 carbonatoms.
 20. The process of claim 19, wherein: a weight ratio of catalystcomponent Ito catalyst component II in the catalyst composition is in arange from about 10:1 to about 1:10; and the olefin monomer is ethylene,and the at least one olefin comonomer comprises 1-butene, 1-pentene,1-hexene, 1-octene, 1-decene, styrene, or any combination thereof. 21.The process of claim 20, wherein the olefin polymer has: a bimodalmolecular weight distribution; or a ratio of Mw/Mn from about 4 to about20; or a number of SCB per 1000 total carbon atoms of the polymer at Mngreater than a number of SCB per 1000 total carbon atoms of the polymerat Mw; or a ratio of the number of SCB per 1000 total carbon atoms ofthe polymer at D90 to the number of SCB per 1000 total carbon atoms ofthe polymer at D10 is in a range from 1.1 to about 10; or a ratio of thenumber of SCB per 1000 total carbon atoms of the polymer at D85 to thenumber of SCB per 1000 total carbon atoms of the polymer at D15 is in arange from 1.1 to about 8; or a MI in a range from about 0.01 to about50 g/10 min; or a ratio of HLMI/MI in a range from about 20 to about 80;or a density in a range from about 0.91 to about 0.945 g/cm³; or anycombination thereof.
 22. The process of claim 21, wherein: the catalystcomposition further comprises at least one organoaluminum compound; andthe at least one activator comprises at least one activator-supportcomprising a solid oxide treated with an electron-withdrawing anion. 23.The process of claim 21, wherein the process is conducted in the absenceof added hydrogen.
 24. The process of claim 21, wherein catalystcomponent I comprises:

or any combination thereof.
 25. The process of claim 21, whereincatalyst component I comprises a meso isomer of:

or any combination thereof.